Ester-terminated poly(ester-amide) in personal care products

ABSTRACT

A resin composition is prepared by reacting components comprising dibasic acid, diamine, polyol and monoalcohol, wherein (a) at least 50 equivalent percent of the dibasic acid comprises polymerized fatty acid; (b) at least 50 equivalent percent of the diamine comprises ethylene diamine; (c) 10-60 equivalent percent of the total of the hydroxyl and amine equivalents provided by diamine, polyol and monoalcohol are provided by monoalcohol; and (d) no more than 50 equivalent percent of the total of the hydroxyl and amine equivalents provided by diamine, polyol and monoalcohol are provided by polyol. This resin composition may be formulated into, for example, personal care products, fragrance releasing products and candles.

This application is a Continuation Application of U.S. patentapplication Ser. No. 10/421,624, entitled “ESTER-TERMINATED POLY(ESTERAMIDES) IN PERSONAL CARE PRODUCTS”, which was filed on Apr. 22, 2003,now U.S. Pat. No. 6,875,245, issued Apr. 5, 2005, which is herebyincorporated, in its entirety, herein by reference.

TECHNICAL FIELD

The invention relates to gelling agents, and in particular to gellantsfor low polarity liquids such as hydrocarbons, and the use thereof incommercial products, e.g., personal care products.

BACKGROUND OF THE INVENTION

Personal care products generally contain one or more active ingredientswithin a carrier formulation. While the active ingredient(s) determinethe ultimate performance properties of the product, the carrierformulation is equally critical to the commercial success of theproduct. The rheology of the carrier (also referred to as the “base”)largely determines the flow properties of the product, and the flowproperties largely determine the manner in which the consumer will applyor use the product.

For example, aluminum chlorohydrate and aluminum-zirconiumtetrachlorohydrex-Gly are metal salts that are commonly used as activeingredients in deodorant and antiperspirant products. Consumers haveshown a preference for applying deodorant from a stick form. Thus, thecarrier in a stick-form deodorant must be a relatively hard substance,and waxy fatty alcohol such as stearyl alcohol has been used as thecarrier in these products. As another example, the active ingredient ina lipstick is the colorant. A lipstick should not be as hard as a stickdeodorant, but of course must maintain its shape when undisturbed atroom temperature. A blend of wax and oil is known to provide aconsistency that is well-suited as a carrier for a lipstick. As a finalexample, shampoo desirably has a viscosity greater than water, and whenthe active ingredient(s) in a shampoo does not have a sufficiently highviscosity, a somewhat viscous carrier material is desirably included inthe shampoo formulation.

From the above examples, it is seen that formulators of personal careproducts depend upon the availability of materials having variousrheological properties, in order to formulate a successful personal careproduct. Materials which have a gel-like character, in that theymaintain their shape when undisturbed but flow upon being rubbed, areoften desired for personal care products.

Transparent (i.e., clear) carriers are needed by formulators who developa personal care product wherein colorant is an active ingredient,because a transparent carrier (as opposed to an opaque carrier) willminimally, if at all, interfere with the appearance of the colorant.However, in recent years consumers have demonstrated an increasingpreference for transparent personal care products such as deodorants andshampoos. There is thus an increasing demand for transparent materialswhich can provide the rheological properties needed for various personalcare products, and particularly which can impart gel-like character to aformulation.

Polyamide resin prepared from polymerized fatty acid and diamine isreported to function as a gellant in formulations developed for personalcare products. For example, U.S. Pat. No. 3,148,125 is directed to aclear lipstick composition formed from polyamide resin compounded with alower aliphatic alcohol and a so-called “polyamide solvent.” Likewise,U.S. Pat. No. 5,500,209 is directed to forming a gel or stick deodorant,where the composition contains polyamide gelling agent and a solventsystem including monohydric or polyhydric alcohols. Thus, the prior artrecognizes to blend certain polyamides with alcohols, to thereby form agel.

Certain modified polyamide resins, e.g., polyamides which are onlypartly amidated but contain esterified carboxyl groups, have beenreported to impart high gel strength and pronounced thixotropicproperties to coating compositions that contain alkyd resins or dryingoils. See U.S. Pat. No. 3,141,767 to Goetze et al. However, the modifiedpolyamide resins of Goetze et al. are not disclosed as being usefulgellants in personal care products, nor useful gellants when a lowpolarity fluid is used as the vehicle.

Low polarity fluids are desirably included in a personal careformulation because they are often transparent, relatively inexpensive,and non-toxic. Low polarity fluids are also available in a wide varietyof viscosities and grades. However, low polarity fluids often do nothave the rheological properties that are desired in a carrier, e.g.,they do not naturally exhibit gel-like character. There is a need in theart for materials that can be combined with low polarity solvent, suchas a hydrocarbon or fatty acid ester, to afford a transparent materialwhich has gel-like character. The gel-like character is preferably of asmooth, silky feeling when the gel is rubbed against the skin. Thepresent invention provides this and related advantages as describedherein.

SUMMARY OF THE INVENTION

In one aspect, the present invention provides a resin compositionprepared by reacting components comprising dibasic acid, diamine, polyoland monoalcohol, wherein

(a) at least 50 equivalent percent of the dibasic acid comprisespolymerized fatty acid; and

(b) at least 50 equivalent percent of the diamine comprises ethylenediamine. Preferably,

(c) 10-60 equivalent percent of the total of the hydroxyl and amineequivalents provided by diamine, polyol and monoalcohol are provided bymonoalcohol; and

(d) no more than 50 equivalent percent of the total of the hydroxyl andamine equivalents provided by diamine, polyol and monoalcohol areprovided by polyol.

In another aspect, the present invention provides a compositioncomprising (a) a resin composition prepared by reacting togethercomponents comprising dibasic acid, diamine, polyol and monoalcohol,wherein at least 50 equivalent percent of the dibasic acid comprisespolymerized fatty acid; and at least 50 equivalent percent of thediamine comprises ethylene diamine; and (b) hydrocarbon; the compositionhaving a consistency of a gel. Preferably, 10-60 equivalent percent ofthe total of the hydroxyl and amine equivalents provided by diamine,polyol and monoalcohol are provided by monoalcohol; and no more than 50equivalent percent of the total of the hydroxyl and amine equivalentsprovided by diamine, polyol and monoalcohol are provided by polyol. Inone aspect of the invention, some or all of the hydrocarbon issubstituted with polydimethylsiloxanes (PDMS) or othersilicon-containing material (such as phenylated silicones such as phenyltrimethicones, phenyl dimethicones and phenyl trimethylsiloxydiphenylsiloxanes etc.).

In another aspect, the present invention provides a compositioncomprising (a) a resin composition prepared by reacting togethercomponents comprising dibasic acid, diamine, polyol and monoalcohol,wherein at least 50 equivalent percent of the dibasic acid comprisespolymerized fatty acid; and at least 50 equivalent percent of thediamine is ethylene diamine; and (b) an ester compound comprising thechemical group —O—C(═O)—, the composition having the consistency of agel. Preferably, 10-60 equivalent percent of the total of the hydroxyland amine equivalents provided by diamine, polyol and monoalcohol areprovided by monoalcohol; and no more than 50 equivalent percent of thetotal of the hydroxyl and amine equivalents provided by diamine, polyoland monoalcohol are provided by polyol.

In another aspect, the present invention provides a compositioncomprising (a) a resin composition prepared by reacting togethercomponents comprising dibasic acid, diamine, polyol and monoalcohol,wherein at least 50 equivalent percent of the dibasic acid comprisespolymerized fatty acid; and at least 50 equivalent percent of thediamine is ethylene diamine; and (b) a polyester compound; thecomposition having a consistency of a gel. Preferably, 10-60 equivalentpercent of the total of the hydroxyl and amine equivalents provided bydiamine, polyol and monoalcohol are provided by monoalcohol; and no morethan 50 equivalent percent of the total of the hydroxyl and amineequivalents provided by diamine, polyol and monoalcohol are provided bypolyol.

In another aspect, the present invention provides a method for preparinga resin composition comprising ester-terminated poly(ester-amide), themethod comprising reacting w equivalents of hydroxyl from polyol or areactive equivalent thereof, x equivalents of carboxylic acid fromdiacid or a reactive equivalent thereof, y equivalents of amine fromdiamine, and z equivalents of hydroxyl from monoalcohol or a reactiveequivalent thereof under reactions conditions to provide a resincomposition having an acid number of less than 20 and an amine number ofless than 20, wherein at least about 50% of the carboxylic acidequivalents are from polymerized fatty acid, at least about 50% of theamine equivalents are from ethylene diamine, and monoalcohol issubstantially the only monofunctional reactant used to form the resin.Preferably, 10-60 equivalent percent of the total of the hydroxyl andamine equivalents provided by diamine, polyol and monoalcohol areprovided by monoalcohol; and no more than 50 equivalent percent of thetotal of the hydroxyl and amine equivalents provided by diamine, polyoland monoalcohol are provided by polyol.

The present invention also provides a personal care product comprising aresin composition prepared by reacting components comprising dibasicacid, diamine, polyol and monoalcohol, wherein (a) at least 50equivalent percent of the dibasic acid comprises polymerized fatty acid;(b) at least 50 equivalent percent of the diamine comprises ethylenediamine; (c) 10-60 equivalent percent of the total of the hydroxyl andamine equivalents provided by diamine, polyol and monoalcohol areprovided by monoalcohol; and (d) no more than 50 equivalent percent ofthe total of the hydroxyl and amine equivalents provided by diamine,polyol and monoalcohol are provided by polyol.

In another aspect, the present invention provides a controlled releasecomposition comprising a volatile component and a resin compositionprepared by reacting components comprising dibasic acid, diamine, polyoland monoalcohol, wherein (a) at least 50 equivalent percent of thedibasic acid comprises polymerized fatty acid; (b) at least 50equivalent percent of the diamine comprises ethylene diamine; (c) 10-60equivalent percent of the total of the hydroxyl and amine equivalentsprovided by diamine, polyol and monoalcohol are provided by monoalcohol;and (d) no more than 50 equivalent percent of the total of the hydroxyland amine equivalents provided by diamine, polyol and monoalcohol areprovided by polyol.

In another aspect, the present invention provides a candle comprising awick and a resin composition prepared by reacting components comprisingdibasic acid, diamine, polyol and monoalcohol, wherein (a) at least 50equivalent percent of the dibasic acid comprises polymerized fatty acid;(b) at least 50 equivalent percent of the diamine comprises ethylenediamine; (c) 10-60 equivalent percent of the total of the hydroxyl andamine equivalents provided by diamine, polyol and monoalcohol areprovided by monoalcohol; and (d) no more than 50 equivalent percent ofthe total of the hydroxyl and amine equivalents provided by diamine,polyol and monoalcohol are provided by polyol; where the candle furthercomprises a solvent that is gelled by the resin.

These and other aspects of the present invention are described infurther detail below.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed to ester-terminated poly(ester-amides)(ETPEA) and a method of preparing a resinous composition (hereinafter,simply “a resin”) comprising, in whole or part, EPTEA. A resincomprising ETPEA (an “ETPEA resin”) is useful as a gelling agent forhydrocarbons and other low polarity liquids, where the resultant gelsare useful components in, for example, personal care products, candles,lubricants, inks, corrosion inhibitors, cosmetic formulations and otherproducts that can benefit from gel-like character.

In one aspect, the present invention provides a resin compositionprepared by reacting components comprising dibasic acid, diamine, polyoland monoalcohol, wherein at least 50 equivalent percent of the dibasicacid comprises polymerized fatty acid; and at least 50 equivalentpercent of the diamine comprises ethylene diamine. Before furtherdescribing this resin, and other aspects of the present invention, thereactants useful in preparing the resin will be described.

The dibasic acid is an organic molecule containing two carboxylic acidgroups or reactive equivalents thereof. A preferred dibasic acid ispolymerized fatty acid, and in particular the dimer acid component ofpolymerized fatty acid. Polymerized fatty acid is typically a mixture ofstructures, including dimer acid and trimer acid, where individual dimeracids may be saturated, unsaturated, cyclic, acyclic, etc. Polymerizedfatty acid as used to form the resin of the invention is a well knownmaterial of commerce, and thus need not be described in great detail.Polymerized fatty acid is typically formed by heating long-chainunsaturated fatty acids, e.g., C₁₈ monocarboxylic acids, to about200-250° C. in the presence of a clay catalyst in order that the fattyacids polymerize. The product typically comprises dimer acid, i.e., C₃₆dicarboxylic acid formed by dimerization of the fatty acid, and trimeracid, i.e., C₅₄ tricarboxylic acid formed by trimerization of the fattyacid. A more detailed discussion of fatty acid polymerization may befound in, e.g., U.S. Pat. No. 3,157,681 and Naval Stores—Production,Chemistry and Utilization, D. F. Zinkel and J. Russell (eds.), Pulp.Chem. Assoc. Inc., 1989, Chapter 23.

Because fatty acid polymerization typically forms much more dimer acidthan trimer acid, those skilled in the art may often refer topolymerized fatty acid as dimer acid, even though some trimer acid, andeven higher polymerization products, may be present with the dimer acid.It is preferred that the polymerized fatty acid contain less than about20 weight percent of trimer acid, based on the total weight of thepolymerized fatty acid, and that the dimer acid constitute at leastabout 80 weight percent of the polymerized fatty acid. More preferably,the dimer acid constitutes essentially all of the polymerized fattyacid.

Typical unsaturated fatty acids used to form polymerized fatty acidinclude oleic acid, linoleic acid, linolenic acid, etc. Tall oil fattyacid, which is a mixture containing long-chain unsaturated fatty acidsobtained as a byproduct of the wood pulping process, is preferred forpreparing polymerized fatty acid useful in the invention. While tall oilfatty acid is a preferred source of long-chain fatty acid, thepolymerized fatty acid may alternatively be prepared by polymerizationof unsaturated fatty acids from other sources, e.g., soybeans or canola.The polymerized fatty acid useful in the invention is a liquid, with anacid number on the order of about 180 to about 200.

The polymerized fatty acid of the invention may be hydrogenated prior tobeing used in the resin-forming reaction of the invention. Hydrogenationtends to provide for a slightly higher melting point for the inventiveresin, as well as provide the resin with greater oxidative and colorstability. Hydrogenated polymerized fatty acid tends to provide for alighter colored resin, and is a preferred polymerized fatty acid for usein the practice of the present invention.

Polymerized fatty acid, dimer acid, and hydrogenated versions thereofmay be obtained from a number of commercial suppliers. For example,Arizona Chemical (Jacksonville, Fla.) sells polymerized fatty acid undertheir UNIDYME® trademark.

In addition to polymerized fatty acid, or reactive equivalents thereof,the dibasic acid may comprise dibasic acid of the formula HOOC—R¹—COOHor reactive equivalents thereof, which may be referred to herein asco-diacid. In one aspect, R¹ contains 4 to 19, preferably about 4 to 12,and more preferably about 4 to 8 carbon atoms. The carbon atoms may bearranged in a linear, branched or cyclic fashion, and unsaturation maybe present between any two carbon atoms. Thus, R¹ may be aliphatic oraromatic. When present, these lower carbon-number R¹ groups arepreferably formed entirely of carbon and hydrogen, i.e., are hydrocarbongroups.

An exemplary co-diacid is a so-called “linear” diacid of the formulaHOOC—R¹—COOH wherein R¹ is a linear C₄₋₁₂ hydrocarbon group, and morepreferably is a linear C₆₋₈ hydrocarbon group. Linear co-diacidssuitable for the present invention include 1,6-hexanedioic acid (adipicacid), 1,7-heptanedioic acid (pimelic acid), 1,8-octanedioic acid(suberic acid), 1,9-nonanedioic acid (azelaic acid), 1,10-decanedioicacid (sebacic acid), 1,11-undecanedoic acid, 1,12-dodecanedioic acid(1,10-decanedicarboxylic acid), 1,13-tridecanedioic acid (brassylicacid) and 1,14-tetradecanedioic acid (1,12-dodecanedicarboxylic acid).

Another exemplary co-diacid for use in the present invention is thereaction product of acrylic or methacrylic acid (or the ester thereof,with a subsequent hydrolysis step to form an acid) and an unsaturatedfatty acid. For example, a C₂₁ diacid of this type may be formed byreacting acrylic acid with a C₁₈ unsaturated fatty acid (e.g., oleicacid), where an ene-reaction presumably occurs between the reactants. Anexemplary C₂₁, diacid is commercially available from WestvacoCorporation, Chemical Division, Charleston Heights, S.C., as theirproduct number 1550.

Aromatic diacids may be used as the co-diacid. An “aromatic diacid” asused herein is a molecule having two carboxylic acid groups (—COOH) orreactive equivalents thereof (e.g., acid chloride (—COCl) or ester(—COOR)) and at least one aromatic ring (“Ar”). Phthalic acids, e.g.,isophthalic acid and terephthalic acid, are exemplary aromatic diacids.The aromatic diacid may contain aliphatic carbons bonded to the aromaticring(s), as in HOOC—CH₂—Ar—CH₂—COOH and the like. The aromatic diacidmay contain two aromatic rings, which may be joined together through oneor more carbon bonds, (e.g., biphenyl with carboxylic acid substitution)or which may be fused (e.g., naphthalene with carboxylic acidsubstitution).

In one aspect, the resin is prepared with co-diacid and the co-diacid isselected from 1,4-cyclohexane dicarboxylic acid, isophthalic acid,adipic acid, azeleic acid, sebacic acid, and dodecandioic acid.

The diamine reactant has two amine groups, both of which are preferablyprimary amines, and is represented by the formulaHN(R^(2a))—R²—N(R^(2a))H. R^(2a) is preferably hydrogen, but may also bean alkyl group or may also join together with R² or another R^(2a) toform a heterocyclic structure. A preferred diamine is ethylene diamine,i.e., a diamine wherein R^(2a) is hydrogen and R² is —CH₂CH₂—.

Diamines other than ethylene diamine may be referred to herein asco-diamines. When present, co-diamines are preferably used in a minoramount compared to the ethylene diamine. In a co-diamine, R² may be ahydrocarbon group having at least three carbon atoms, where the carbonatoms may be arranged in a linear, branched or cyclic fashion, and thegroup may be saturated or contain unsaturation. Thus, R² may bealiphatic or aromatic. Preferred R² hydrocarbon groups in the co-diaminehave 2 to 36 carbon atoms, more preferred R² hydrocarbon groups have 2to 12 carbon atoms, and still more preferred hydrocarbon groups have 2to 6 carbon atoms.

Exemplary co-diamines having hydrocarbon R² groups include, withoutlimitation, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane,1,2-diamino-2-methylpropane, 1,3-diaminopentane, 1,5-diaminopentane,2,2-dimethyl-1,3-propanediamine, 1,6-hexanediamine (also known ashexamethylenediamine, HMDA), 2-methyl-1,5-pentanediamine,1,7-diaminoheptane, 1,8-diaminooctane, 2,5-dimethyl-2,5-hexanediamine,1,9-diaminononane, 1,10-diaminodecane, 1,12-diaminododecane,diaminophenanthrene (all isomers, including 9,10),4,4′-methylenebis(cyclohexylamine), 2,7-diaminofluorene, phenylenediamine (1,2; 1,3 and/or 1,4 isomers), adamantane diamine,2,4,6-trimethyl-1,3-phenylenediamine, 1,3-cyclohexanebis(methylamine),1,8-diamino-p-menthane, 2,3,5,6-tetramethyl-1,4-phenylenediamine,diaminonaphthalene (all isomers, including 1,5; 1,8; and 2,3) and4-amino-2,2,6,6-tetramethylpiperidine.

Suitable aromatic co-diamines (by which is meant molecules having tworeactive, preferably primary amine groups (—NH₂) and at least onearomatic ring (“Ar”) include xylene diamine and naphthalene diamine (allisomers).

The R² group of the co-diamine may contain oxygen atoms in the form of apolyalkylene oxide group. Exemplary polyalkylene oxide-based co-diaminesinclude, without limitation, the JEFFAMINE™ diamines, i.e.,poly(alkyleneoxy)diamines from Huntsman Chemical (Salt Lake City, Utah),also known as polyether diamines. Preferred polyalkyleneoxide-containing co-diamines are the JEFFAMINE® ED, XTJ and D seriesdiamines. Ether-containing R² groups are not preferred, as they tend tolower the melting point of the resin to an undesirable extent. However,small amounts of a polyalkylene oxide-based co-diamine with a majoramount of ethylene diamine are suitable for use in the invention

The R² group of the co-diamine may contain nitrogen atoms, where thesenitrogen atoms are preferably secondary or tertiary nitrogen atoms. Atypical nitrogen atom-containing R² group having secondary nitrogenatoms is a polyalkylene amine, i.e., a group containing alternatingalkylene groups and amine groups (i.e., —NH— groups). The alkylene groupis preferably ethylene, i.e., —CH₂CH₂—, and the polyalkylene amine maybe represented by the formula NH₂—(CH₂CH₂NH)_(m)CH₂CH₂—NH₂ wherein m isan integer from 1 to about 5. Diethylenetriamine (DETA) andtriethylenetetraamine (TETA) are representative examples. When thediamine contains two primary amines in addition to secondary amines, theEPTEA-forming reaction is preferably conducted at relatively lowtemperature, so that the primary amines (in preference to the secondaryamines) react with the diacid component.

However, the nitrogen atoms in the nitrogen-containing R² group may alsobe present as tertiary nitrogen atoms, e.g., they may be present in aheterocycle of the formula:

wherein R_(c) is a C₁₋₃ alkyl group. Bis(aminoethyl)-N,N′-piperazine andbis(aminopropyl)-N,N′-piperazine may be used to introduce these R²groups into an ETPEA molecule, and these are such co-diamines accordingto the invention. In addition, the co-diamine may have one primary aminegroup and one secondary amine group (e.g., N-ethylethylenediamine or1-(2-aminoethyl)piperazine). Generally, it is preferred that aminecompounds having secondary amines not be present in the reaction mixtureto any great extent, because their incorporation into an esterterminated polyamide tends to provide for poorer gelling ability of theester-terminated polyamide.

In general, the diamine reactant may have the formulaHN(R^(2a))—R²—NH(R^(2a)) wherein R^(2a) is preferably hydrogen, but mayalso be C₁₋₁₀ alkyl, preferably C₁₋₅alkyl, and more preferablyC₁₋₃alkyl. In addition, R^(2a) may join together with R² or anotherR^(2a) group to form a heterocyclic structure. For example, whenpiperazine is used as a co-diamine, the two R^(2a) groups in theHN(R^(2a))—R²—NH(R^(2a)) structure have joined together to form anethylene bridge.

In one aspect, the ETPEA resin of the invention is prepared fromco-diamine, where the co-diamine is selected from 1,6-hexanediamine,xylenediamine, 1,2-propanediamine, 2-methylpentamethylenediamine, and1,12-dodecanediamine. Suitable diamines of the present invention areavailable from a number of commercial sources including Aldrich(Milwaukee, Wis.; http://www.aldrich.sial.com); EM Industries, Inc.(Hawthorne, N.Y.; http://www.emscience.com); Lancaster Synthesis, Inc.(Windham, N.H.; http://www.lancaster.co.uk); Spectrum Quality Product,Inc. (New Brunswick, N.J.; http://www.spectrumchemical.com).

The monoalcohol may be represented by the formula R³—OH, wherein R³ ispreferably a hydrocarbon group having at least ten carbon atoms. Thus,the monoalcohol can also be described as a monohydric alcohol. In oneaspect, R³ is a C₁₀₋₃₀ hydrocarbon, preferably a C₁₂₋₂₄ hydrocarbon,still more preferably is a C₁₆₋₂₂ hydrocarbon, and yet still morepreferably is a C₁₈ hydrocarbon. As used herein, the term C₁₀₋₃₀hydrocarbon refers to a hydrocarbon group having at least 10, but notmore than 30 carbon atoms, and similar terms have an analogous meaning.The carbon atoms of the hydrocarbon group may be arranged in a linear,branched or cyclic fashion, and the group may be saturated orunsaturated. However, in one aspect of the present invention, R³ islinear, with the hydroxyl group located on a terminal carbon atom, i.e.,the monoalcohol is a primary monoalcohol. Thus, 1-dodecanol,1-tetradecanol, 1-hexadecanol (cetyl alcohol), 1-octadecanol (stearylalcohol), 1-eicosanol (arachidyl alcohol) and 1-docosanol (behenylalcohol) are preferred monoalcohols for preparing resins of theinvention, where names in parentheses are common or trivial names bywhich these monoalcohols are known. While the monoalcohol has beenexemplified with saturated alkyl groups, the monoalcohol mayalternatively contain an alkenyl group, i.e., an alkyl group havingunsaturation between at least any two adjacent carbon atoms. One or amixture of these alcohols may be used to prepare a resin of theinvention.

Another monoalcohol reactant suited for the invention is a so-calledGuerbet alcohol. Guerbet alcohols have the general formulaH—C(Ra)(Rb)—CH₂—OH wherein Ra and Rb may be the same or different andpreferably represent a C₆₋₁₂ hydrocarbon group. Further discussion ofGuerbet alcohols may be found in, e.g., “Dictionary For Auxiliaries ForPharmacy, Cosmetics And Related Fields,” H. P. Fiedler, 3^(rd) Ed.,1989, Cantor Aulendorf. 2-Hexadecyloctadecanol, which has 24 carbonatoms, is a preferred Guerbet alcohol for use in the present invention.

Another suitable monoalcohol reactant is a linear wax alcohol. Suitablelinear wax alcohols are commercially available from, e.g., PetroliteCorporation (Tulsa, Okla.) under their UNILIN® trademark. These waxalcohols are typically a blend of linear alcohols having at least about20 carbon atoms, and more typically at least about 24 carbon atoms.Vapor pressure osmometry (VPO), among many other techniques, may be usedto characterize the number average molecular weight of a blend ofalcohols. In one aspect, the mixture of monohydric linear wax alcoholshas a number average molecular weights by VPO of about 200 to about 800,preferably about 300 to about 600. Pure C₂₂ monohydric linear alcoholhas a molecular weight of 326 by VPO.

The monohydric alcohol, whether present as an essentially pure alcoholor in a mixture of monohydric alcohols, preferably has a straight chainalkyl group. Exemplary alcohols useful in the invention include1-eicosanol (C₂₀), 1-docosanol (C₂₂, also known as behenyl alcohol),dotriacontanol (C₃₂), tetratriacontanol (C₃₄), pentatriacontanol (C₃₅),tetracontanol (C₄₀), tetraacontanol (C₄₄), dopentaacontanol (C₅₄),tetrahexaacontanol (C₆₄), dohexaacontanol (C₇₂), etc.

A final ingredient necessary in preparing an ETPEA resin of the presentinvention is polyol, which may also be referred to as polyhydricalcohol. The polyol is of the formula R⁴(OH)_(n) wherein R⁴ is ann-valent organic group. For instance, R⁴ may be a C₂-C₂₀ organic groupwithout hydroxyl substitution. As another example, R⁴ may be ahydrocarbon. Typically, n is selected from 2, 3, 4, 5 and 6. Suitablepolyols for use in preparing an ETPEA resin of the present inventioninclude ethylene glycol, propylene glycol, butylene glycol, glycerol,trimethylolpropane, pentaerythritol, neopentyl glycol,tris(hydroxylmethyl)methanol, di-pentaerythritol, andtri-pentaerthyritol.

Reactive equivalents of diacids and/or diamines may be used in theinvention. For example, diesters may be substituted for some or all ofthe diacid, where “diesters” refer to the esterification product ofdiacid with hydroxyl-containing molecules. However, such diesters arepreferably prepared from relatively volatile hydroxyl-containingmolecules, in order that the hydroxyl-containing molecule may be easilyremoved from the reaction vessel subsequent to monoalcohol and/ordiamine (both as defined herein) reacting with the diester. A loweralkyl diester, e.g., the esterification or diesterification product ofdiacid as defined herein and a C₁₋₄ monohydic alcohol (e.g., methanol,ethanol, propanol and butanol), may be used in place of some or all ofthe diacid in the ETPEA-resin forming reaction of the invention. Theacid halide of the diacid may likewise be employed in place of some orall of the diacid, however such a material is typically much moreexpensive and difficult to handle compared to the diacid, and thus thediacid is preferred. Likewise, the monoalcohol may be esterified with avolatile acid, e.g., acetic acid, prior to being employed in the ETPEAresin-forming reaction of the invention. While such reactive equivalentsmay be employed in the reaction, their presence is not preferred becausesuch equivalents introduce undesired reactive groups into the reactionvessel.

In preparing a resin of the invention, the above-described reactants maybe combined in any order. Preferably, the reactants are simply mixedtogether and heated for a time and at a temperature sufficient toachieve essentially complete reaction, to thereby form the inventiveresin. The terms “complete reaction” and “reaction equilibrium” as usedherein have essentially the same meaning, namely that further heating ofthe product resin does not result in any appreciable change in theperformance characteristics of the product resin, where the mostrelevant performance characteristic is the ability of the product resinto form a clear, firm gel upon being combined with a solvent (asmentioned above and discussed further below).

Thus, the ETPEA resin may be formed in a one-step procedure, wherein allof the dibasic acid, diamine, polyol and monoalcohol (includingco-diacid and co-diamine, if present) are combined and then heated toabout 200-250° C. for a few hours, typically 2-8 hours. As one or moreof the reactants may be a solid at room temperature, it may beconvenient to combine each of the ingredients at a slightly elevatedtemperature, and then form a homogeneous mixture prior to heating thereaction mixture to a temperature sufficient to cause reaction betweenthe dibasic acid, diamine, polyol and monoalcohol. Alternatively,although less preferably, two or three of the reactants may be combinedand reacted together, and then the remaining reactant(s) is/are addedfollowed by further heating the desired product is obtained. Reactionprogress may be conveniently monitored by periodically measuring theacid and/or amine number of the product mixture.

Any catalyst that may accelerate amide formation between carboxylic acidand amine groups, and/or ester formation between carboxylic acid andhydroxyl groups, may be present in the reaction mixture described above.Thus, mineral acid such as phosphoric acid, or tin salts such asdibutyltin oxide, may be present during the reaction. In addition, it ispreferred to remove water from the reaction mixture as it is formed uponamide and ester formation. This is preferably accomplished bymaintaining a vacuum on the reacting mixture.

It is important to control the stoichiometry of the reactants in orderto prepare ester-terminated poly(ester-amides) according to theinvention. In the following discussion regarding reactant stoichiometry,the terms “equivalent(s)” and “equivalent percent” will be used, and areintended to have their standard meanings as employed in the art.However, for additional clarity, it is noted that equivalents refer tothe number of reactive groups present in a molar quantity of a molecule,such that a mole of a dibasic acid (e.g., sebacic acid) has twoequivalents of carboxylic acid, while a mole of monoalcohol has oneequivalent of hydroxyl. Furthermore, it is emphasized that the dibasicacid has only two reactive groups (both carboxylic acids), themonoalcohol has only one reactive group (a hydroxyl group), the diaminehas only two reactive groups (preferably both primary amines), and thepolyol has at least two reactive groups (i.e., at least two reactivehydroxyl groups) and these are preferably, although not necessarily, theonly reactive materials present in the reaction mixture.

According to the invention, is it preferred that the equivalents ofcarboxylic acid are substantially equal to the combined equivalents ofhydroxyl contributed by monoalcohol and polyol, and amine contributed bydiamine. In other words, if the reaction mixture used to form an ETPEAresin has “x” equivalents of carboxylic acid, “y” equivalents of amineand “z” equivalents of hydroxyl (from the combination of monoalcohol andpolyol), then 0.9≦{x/(y+z)}≦1.1, and preferably {x/(y+z)} issubstantially 1.0. Under these conditions, substantially all of thecarboxylic acid groups will react with substantially all of the hydroxyland amine groups, so that the final product contains very littleunreacted carboxylic acid, hydroxyl or amine groups. In other words,each of the acid and amine numbers of a resin of the invention ispreferably less than about 25, is more preferably less than about 15,and is more preferably less than about 10, and is still more preferablyless than about 5.

When co-diacid is employed to prepare an ETPEA resin, the co-diacidpreferably contributes no more than about 50% of the equivalents ofcarboxylic acid present in the reaction mixture. Stated another way, theco-diacid contributes from 0-50 equivalent percent of the acidequivalents in the reaction mixture. Preferably, the co-diacidcontributes 0-25 equivalent percent, and more preferably contributes0-10 equivalent percent of the acid equivalents in the reaction mixture.

When co-diamine is employed to prepare an ETPEA resin, the co-diaminepresent in the reaction mixture preferably contributes no more thanabout 50% of the equivalents of amine present in the reaction mixtureStated another way, the co-diamine contributes from 0-50 equivalentpercent of the amine equivalents in the reaction mixture. Preferably,the co-diamine contributes 0-25 equivalent percent, and more preferablycontributes 0-10 equivalent percent of the amine equivalents in thereaction mixture.

The stoichiometry of the reactants will have a significant impact on thecomposition and properties of the ETPEA resin. For example, ETPEA resinsmade with increasing amounts of monoalcohol will tend to have loweraverage molecular weights. In other words, as more monofunctionalreactant is used, the number of amide pairs in an average ETPEA moleculeof the resin will tend to decrease. On the other hand, as lessmonoalcohol is used, the average molecular weight of the ETPEA in theresulting resin will increase. In general, increasing the averagemolecular weight for the ETPEAs in a resin will tend to increase themelting point and melt viscosity of the resin, which tends to provide afirmer gel when the ETPEA resin is combined with a low polarity liquid.However, when the average molecular weight of the ETPEA increases to acertain point, the EPTEA resins become insoluble in low polaritysolvents, and therefore do not form desirable gels. Therefore, in apreferred aspect of the invention, the monoalcohol level in thereactants should be such that at least 10 equivalent percent of thetotal amine and hydroxyl equivalents should be derived from monoalcohol.

The amount of polyol used in the reactant formulation will also have animpact on the properties of the ETPEA resin. Increasing the level ofpolyol relative to the other reactants tends to decrease the softeningpoint of the ETPEA resin. When the polyol contributes greater than about50 equivalent percent of the total equivalents of hydroxyl and aminegroups present in the ETPEA-forming reaction mixture, then the resultingETPEA resin becomes undesirably “soft” and mixtures of this soft resinwith a low polarity fluid tends to form more of a viscous oil than agel. Accordingly, in one aspect of the invention, the hydroxylequivalents from polyol are less than or equal to 50% of the totalhydroxyl and amine equivalents contributed by the total of the polyol,monoalcohol and diamine reactants. In other aspects, the hydroxylequivalents from polyol are less than or equal to 40%, or 30% or 20%, ofthe total hydroxyl and amine equivalents contributed by the total of thepolyol, monoalcohol and diamine reactants.

In one aspect of the invention, the amine equivalents from diamine equal0.3 to 0.75 of the total amine and hydroxyl equivalents provided bydiamine, polyol and monoalcohol. In another aspect, the hydroxylequivalents from polyol equals 0.05 to 0.45 of the total amine andhydroxyl equivalents provided by diamine, polyol and monoalcohol. Inanother aspect, the hydroxyl equivalents from monoalcohol equals 0.20 to0.45 of the total amine and hydroxyl equivalents provided by diamine,polyol and monoalcohol.

For example, in one aspect the invention provides a resin prepared asdescribed herein where the amine equivalents from diamine equals 0.30 to0.75 of the total amine and hydroxyl equivalents provided by diamine,polyol and monoalcohol; the hydroxyl equivalents from polyol equals 0.05to 0.45 of the total amine and hydroxyl equivalents provided by diamine,polyol and monoalcohol; and the hydroxyl equivalents from monoalcoholequals 0.20 to 0.45 of the total amine and hydroxyl equivalents providedby diamine, polyol and monoalcohol. As another example, the presentinvention provides a resin prepared by reacting dibasic acid, diamine,polyol and monoalcohol where polymerized fatty acid constitutes at least60 equivalent percent of the acid equivalents of the dibasic acid,ethylene diamine constitutes at least 75 equivalent percent of the amineequivalents of the amine; the amine equivalents from diamine equals 0.30to 0.75 of the total amine and hydroxyl equivalents provided by diamine,polyol and monoalcohol; the hydroxyl equivalents from polyol equals 0.05to 0.45 of the total amine and hydroxyl equivalents provided by diamine,polyol and monoalcohol; and the hydroxyl equivalents from monoalcoholequals 0.20 to 0.45 of the total amine and hydroxyl equivalents providedby diamine, polyol and monoalcohol.

In one aspect, the present invention provides a method for preparing aresin composition comprising ester-terminated poly(ester-amide), themethod comprising reacting w equivalents of hydroxyl from polyol or areactive equivalent thereof, x equivalents of carboxylic acid fromdiacid or a reactive equivalent thereof, y equivalents of amine fromdiamine, and z equivalents of hydroxyl from monoalcohol or a reactiveequivalent thereof under reactions conditions to provide a resincomposition having an acid number of less than 20 and an amine number ofless than 20, wherein at least about 60% of the carboxylic acidequivalents are from polymerized fatty acid, at least about 60% of theamine equivalents are from ethylene diamine, and monoalcohol issubstantially the only monofunctional reactant used to form the resin.In a preferred embodiment, w/(w+y+z) is within the range of about 0.05to 0.60; y/(w+y+z) is within the range of about 0.20 to 0.75; andz/(w+y+z) is within the range of 0.20 to 0.50.

As stated above, the ester-terminated poly(ester-amides) describedherein are useful in forming gels with solvents at room temperature, andaccordingly preferably have a softening point greater than roomtemperature. A precise definition of “gel” is not easy to give, althoughmost if not all researchers recognize a “gel.” Generally, a gel is moreviscous than a liquid or paste, and retains its shape when leftundisturbed, i.e., is self-supporting. However, a gel is not as hard orfirm as a stick or wax. Gels may be penetrated more easily than awax-like solid, where “hard” gels are relatively more resistant topenetration than “soft” gels.

Almdale et al. (Polymer Gels and Networks, Vol. 1, No. 5 (1993)) listtwo criteria for defining a system as a gel: (1) a gel consists of twoor more components, one of which is a liquid, present in substantialquantities; and (2) a gel is a soft material which is solid orsolid-like. This latter requirement can be described more accuratelythrough rheological measurement. Typically, gels possess a storagemodulus G′(w) which exhibits a pronounced plateau at higher frequencies(on the order of 1-100 radians/second), and a loss modulus G″(w) whichis considerably smaller than the storage modulus in the plateau region.In a strict sense, the term “gel” applies to systems having a valueG′(w) that is higher than its value of G″(w) at low frequencies. Many ofthe compositions according to the present invention are gels by one orboth of the above definitions. A gel is free-standing or self-supportingin that its yield value is greater than the sheer stress imposed bygravity.

Accordingly, another aspect of the invention is a gel formed betweeningredients comprising ester-terminated poly(ester-amide) as describedabove and a non-aqueous liquid, preferably a low-polarity liquid. Apreferred low polarity liquid is a hydrocarbon, with preferredhydrocarbons being solvents and oils. Solvents and oils may bedistinguished in that defatting occurs when solvents are rubbed on humanskin, leading to drying and irritation. However, defatting does notoccur when oils are rubbed on human skin. Oils are more preferred thansolvents in most personal-care formulations, and thus are preferred informing the gels of the present invention. Preferably, the hydrocarbonhas a relatively high number of carbon atoms, e.g., 10 to 30 carbonatoms, and thus is not a volatile hydrocarbon.

A preferred oil is mineral oil, also sometimes referred to as medicinaloil. Mineral oil is a highly refined, colorless, tasteless, and odorlesspetroleum oil (i.e., derived by processing petroleum/crude oil) usedmedicinally as an internal lubricant and for the manufacture of salvesand ointments. Such mineral oils are highly refined in havingsubstantially all volatile hydrocarbons removed therefrom, and in beinghydrogenated (also called hydrotreated) in order to remove substantiallyall unsaturation, e.g., aromatic groups have been reduced to the fullysaturated analog. A preferred mineral oil to prepare a gel of theinvention is so-called “white” mineral oil, which is water-white (i.e.,colorless and transparent) and is generally recognized as safe forcontact with human skin. Mineral oil may also be characterized in termsof its viscosity, where light mineral oil is relatively less viscousthan heavy mineral oil, and these terms are defined more specifically inthe U.S. Pharmacopoeia, 22^(nd) revision, p. 899 (1990). Any mineral oilmay be used in the invention to form a gel.

Other hydrocarbons that may be used in the invention include relativelylower molecular weight hydrocarbons including linear saturatedhydrocarbons such a tetradecane, hexadecane, octadecane, etc. Cyclichydrocarbons such as decahydronaphthalene (DECALIN), fuel gradehydrocarbons, branched chain hydrocarbons such as PERMETHYL fromPermethyl Corporation and ISOPAR from Exxon Corp., and hydrocarbonmixtures such as product PD-23 from Witco (Greenwich, Conn.) may also beused in preparing gels of the invention. Such hydrocarbons, particularlysaturated hydrocarbon oils, are a preferred liquid for preparing a gelof the invention because such hydrocarbons are often less irritating tothe skin than liquids containing aromatic, ketone and other functionalgroups.

Another class of suitable low polarity liquids are esters, andparticularly esters of fatty acids. Such esters may be monofunctionalesters (i.e., have a single ester moiety) or may be polyfunctional(i.e., have more than one ester group). Suitable esters include, but arenot limited to, the reaction products of C₁₋₂₄ monoalcohols with C₁₋₂₂monocarboxylic acids, where the carbon atoms may be arranged in alinear, branched and/or cyclic fashion, and unsaturation may optionallybe present between carbon atoms. Preferably, the ester has at leastabout 18 carbon atoms. Examples include, but are not limited to, fattyacid esters such as isopropyl isostearate, n-propyl myristate, isopropylmyristate, n-propyl palmitate, isopropyl palmitate, hexacosanylpalmitate, octacosanyl palmitate, triacontanyl palmitate, dotriacontanylpalmitate, tetratriacontanyl palmitate, hexacosanyl stearate,octacosanyl stearate, triacontanyl stearate, dotriacontanyl stearate andtetratriacontanyl stearate; salicylates, e.g., C₁₋₁₀ salicylates such asoctyl salicylate, and benzoate esters including C₁₂₋₁₅ alkyl benzoate,isostearyl benzoate and benzyl benzoate.

Suitable esters are those commonly employed in the cosmetics industryfor the formulation of lipstick and make-up, e.g., the fatty acid estersmentioned above, and are often denoted as “cosmetic esters.” Othercosmetic esters include glycerol and propylene glycol esters of fattyacids, including the so-called polyglycerol fatty acid esters andtriglycerides. Exemplary cosmetic esters include, without limitation,propylene glycol monolaurate, polyethylene glycol (400) monolaurate,castor oil, triglyceryl diisostearate and lauryl lactate. Thus, theliquid may have more than one of ester, hydroxyl and etherfunctionality. For example, C₁₀₋₁₅ alkyl lactate may be used in a gel ofthe invention. In addition, esterified polyols such as the polymersand/or copolymers of ethylene oxide, propylene oxide and butylene oxidereacted with C₁₋₂₂ monocarboxylic acids are useful. The carbon atoms ofthe C₁₋₂₂ monocarboxylic acids may be arranged in a linear, branchedand/or cyclic fashion, and unsaturation may be present between thecarbon atoms. Preferred esters are the reaction product of an alcoholand a fatty acid, where the alcohol is selected from C₁₋₁₀ monohydricalcohol, C₂₋₁₀ dihydric alcohol and C₃₋₁₀ trihydric alcohol, and thefatty acid is selected from a C₈₋₂₄ fatty acid.

The gels of the invention preferably do not contain substantial amountsof unreacted monoalcohol, i.e., monohydric alcohols having a singlehydroxyl and their only functional group. Thus, the gels of theinvention preferably contain less than 25 weight percent, morepreferably less than 10 weight percent, and still more preferably lessthan 5 weight percent of unreacted monoalcohol.

The gels of the invention are preferably self-supporting, in that theyretain their shape at room temperature and in the absence of shear.Also, the inventive gels are preferably clear or translucent. The termsclear, transparent and clarity are intended to have their ordinarydictionary definitions; thus, a clear gel allows ready viewing ofobjects behind it. By contrast, a translucent gel, although allowinglight to pass through, causes the light to be so scattered that it willbe impossible to see clearly objects behind the translucent stick. Asused herein, a gel is transparent or clear if the maximum transmittanceof light of any wavelength in the range 400 to 800 nm through a sample 1cm thick is at least 35%, preferably at least 50% (see, e.g., EuropeanPatent Publication No. 291,334 A4). The gel is translucent if themaximum transmittance of such light through the sample is between 2% andless than 35%. The transmittance can be measured by placing a sample ofthe aforementioned thickness into a light beam of a spectrophotometerwhose working range includes the visible spectrum, such as a Bausch &Lomb Spectronic 88 Spectrophotometer.

The gels of the invention preferably do not display syneresis. Asdefined in the McGraw-Hill Dictionary of Scientific and Technical Terms(3^(rd) Edition), syneresis is the spontaneous separation of a liquidfrom a gel or colloidal suspension due to contraction of the gel.Typically, syneresis is observed as the separation of liquid from a gel,and is sometimes referred to as “bleeding,” in that wetness is seenalong the surfaces of a gel that displays syneresis. From a commercialpoint of view, syneresis is typically an undesirable property, and thegels of the present invention desirably, and surprisingly do not exhibitsyneresis.

To prepare a gel of the invention, an ester-terminated poly(ester-amide)resin is combined with a liquid. The two ingredients are taken toelevated temperature, e.g., up to about 80-150° C., until the resincompletely dissolves in the liquid. A lower temperature may be used if asolution can be prepared at the lower temperature. Upon cooling, themixture forms the gel of the invention. Preferably, the liquid is alow-polarity liquid as described above, and more preferably the liquidis a hydrocarbon. The liquid may contain more than one component, e.g.,hydrocarbon as well as ester-containing material. In any event, theester-terminated poly(ester-amide) is combined with the liquid such thatthe weight percent of ETPEA in the ETPEA+ solvent mixture is about5-50%, and preferably is about 10-45%. Such gels may be transparent,translucent or opaque, depending on the precise identities of theester-terminated poly(ester-amide) and liquid, as well as theconcentration of ETPEA in the mixture.

A commercially desirable aspect of the invention is that the gel may be(although need not be) essentially transparent. Thus, the gels aredesirably combined with colorants, as well as other ingredients, to formlipstick and other cosmetic products. The advantage of a clear gel inthese applications is that the gel imparts little if any undesirablecolor to the lipstick or cosmetic. The gels may be combined withaluminum zirconium salts, as well as other ingredients, to formcolorless underarm deodorant/antiperspirant, which is currently quitepopular. The gels of the invention are also useful in other personalcare products, e.g., cosmetics such as eye make-up, lipstick, foundationmake-up, costume make-up, as well as baby oil, make-up removers, bathoil, skin moisturizers, sun care products, lip balm, waterless handcleaner, medicated ointments, ethnic hair care products, perfume,cologne, and suppositories. In addition, the gels may be used inhousehold products such as automobile wax/polish, candles, furniturepolish, metal cleaners/polishes, household cleaners, paint strippers andinsecticide carriers.

The gels may also be used in industrial products such as fuels (sterno,lighters), toilet bowl rings, lubricants/greases, wire rope lubricant,joint and cable fillers, soldering flux, buffing compounds, crayons andmarkers, modeling clay, rust preventatives, printing inks,protective/removable coatings, and jet inks. For example, a hydrocarbonoil gelled with an ETPEA resin of the invention may be used as a heatsource in, e.g., a cooking apparatus used in camping and hiking. Such acomposition will not flow if tilted, and thus may be safer and neaterthan similar products made from flowing materials.

Formulations to prepare such materials are well known in the art. Forexample, U.S. Pat. Nos. 3,615,289, 3,645,705, 6,111,055, 6,129,771 and6,214,063 describe the formulation of candles and pigmented objectsembedded in candles referred in the art as “icons.” U.S. Pat. Nos.3,148,125 and 5,538,718 describe the formulation of lipstick and othercosmetic sticks. U.S. Pat. Nos. 4,275,054, 4,937,069, 5,069,897,5,102,656 and 5,500,209 each describe the formulation of deodorantand/or antiperspirant. Each of these U.S. Patents is hereby incorporatedfully herein by reference.

The ETPEA resin of the invention may be incorporated into commercialproducts such as those listed above by blending the ETPEA resin with theother components of the product. Typically, the ETPEA resin will bepresent at a concentration of about 1% to about 50% of the composition,based on the total weight of the composition. It is a routine matter tooptimize the amount of ETPEA resin to have present in a composition, andindeed the amount will vary depending on the actual product and thedesired consistency of the product. In general, as more ETPEA resin isused in a formulation, the product will display a more pronounced gelcharacter.

In one aspect, the present invention provides a composition, inparticular a physiologically acceptable composition, comprising at leastone liquid fatty phase structured with ETPEA, combined with at least oneamphiphilic compound with a hydrophilic/lipophilic balance (HLB) valueof, in various embodiments of the invention, less than 16, less than 14,less than 12, less than 10, less than 9, less than 8, less than 7, lessthan 6. This composition can be in the form of, e.g., a stick oflipstick. Wax is optionally present in the composition: in one aspectwax is present, while in another aspect wax is absent. The compositiondemonstrates good impact strength and, when applied to a surface,provides a glossy, non-migrating deposit.

For example, the present invention provides a structured compositioncomprising: (a) at least one liquid fatty phase comprising: (i) ETPEA;and (ii) at least one amphiphilic compound which is liquid at roomtemperature and which has an HLB value of less than 16, preferably lessthan 8. One or more of the following features may optionally be used tocharacterize the composition and/or components thereof:

(a) the at least one amphiphilic compound comprises at least onelipophilic part bonded to at least one polar part; where optionally

-   -   i) the at least one lipophilic part comprises a carbon-based        chain comprising at least 8 carbon atoms; or    -   ii) the at least one lipophilic part comprises from 16 to 32        carbon atoms; or    -   iii) the at least one lipophilic part comprises from 18 to 28        carbon atoms;    -   iv) the at least one polar part is chosen from compounds derived        from alcohols comprising from 1 to 12 hydroxyl groups, polyol        groups comprising from 2 to 12 hydroxyl groups, and        polyoxyalkylene groups comprising at least 2 oxyalkylene units;        where optionally the polyoxyalkylene groups are chosen from        polyoxyalkylene groups which comprise from 0 to 20 oxypropylene        units and from 0 to 20 oxyethylene units.

(b) the at least one amphiphilic compound is chosen from esters whereoptionally

-   -   the esters are chosen from hydroxystearates of glycerol, oleates        of glycerol, isostearates of glycerol, hydroxystearates of        sorbitan, oleates of sorbitan, isostearates of sorbitan,        hydroxystearates of methylglucose, oleates of methylglucose,        isostearates of methylglucose, hydroxystearates of branched C₁₂        to C₂₆ fatty alcohols, oleates of branched C₁₂ to C₂₆ fatty        alcohols and isostearates of branched C₁₂ to C₂₆ fatty alcohols;        where optionally the branched C₁₂ to C₂₆ fatty alcohols are        chosen from octyldodecanols.    -   the esters are chosen from monoesters and diesters.

(c) the at least one amphiphilic compound is present in a concentrationranging from 0.1% to 35% by weight of the total weight of saidcomposition, or is present in a concentration ranging from 2% to 15% byweight of the total weight of said composition.

(d) the at least one structuring polymer is present in a concentrationranging from 0.5% to 80% by weight of the total weight of thecomposition, or is present in a concentration ranging from 5% to 40% byweight of the total weight of said composition.

(e) the at least one liquid fatty phase comprises greater than 40% byweight of the total weight of said at least one liquid fatty phase of atleast one apolar oil; or optionally the at least one liquid fatty phasecomprises greater than 50% by weight of the total weight of said atleast one liquid fatty phase of at least one apolar oil.

(f) the at least one liquid fatty phase comprises at least one oil,where optionally the at least one oil is chosen hydrocarbon-based oilsof mineral origin and hydrocarbon-based oils of synthetic origin.

(g) the at least one liquid fatty phase comprises at least one apolaroil, where optionally the at least one apolar oil is chosen from parleamoil, isoparaffins and squalane.

(h) the at least one liquid fatty phase is present in a concentrationranging from 5% to 99% by weight of the total weight of saidcomposition, or optionally the at least one liquid fatty phase ispresent in a concentration ranging from 20% to 75% by weight of thetotal weight of said composition.

(i) the composition further comprises at least one suitable additivechosen from water optionally thickened or gelled with an aqueous-phasethickener or gelling agent, antioxidants, essential oils, preservingagents, fragrances, neutralizing agents, liposoluble polymers,cosmetically active agents, dermatologically active agents and waxes.

(j) the composition is in a form chosen from a paste, a solid, a cream,an oil-in-water emulsion, a water-in-oil emulsion and an anhydrous gel,optionally translucent or transparent.

(k) the composition further comprises at least one pigment.

(l) the at least one amphiphilic compound has an HLB value ranging from1 to 16, or ranging from 1 to 10, or ranging from 1 to 7, or rangingfrom 1 to 5, or ranging from 3 to 12, or ranging from 3 to 5.

(m) the at least one structuring polymer further comprises a polymerresulting from at least one polycondensation reaction between at leastone dicarboxylic acid comprising at least 32 carbon atoms and at leastone diamine comprising at least 2 carbon atoms, where, in furtheroptional embodiments:

-   -   i) the at least one dicarboxylic acid comprises from 32 to 44        carbon atoms; and/or    -   ii) the said at least one diamine comprises from 2 to 36 carbon        atoms; and/or    -   iii) the at least one dicarboxylic acid is chosen from dimers of        at least one fatty acid comprising at least 16 carbon atoms;        and/or    -   iv) the at least one fatty acid is chosen from oleic acid,        linoleic acid and linolenic acid; and/or    -   v) the at least one diamine is chosen from ethylenediamine,        hexylenediamine, hexamethylenediamine, phenylenediamine and        ethylenetriamine; and/or    -   vi) the at least one structuring polymer comprises a polymer        comprising one or two terminal carboxylic acid groups, where        these terminal groups are optionally esterified with at least        one alcohol chosen from monoalcohols comprising at least 4        carbon atoms (e.g., at least one alcohol is chosen from        monoalcohols comprising from 10 to 36 carbon atoms, or at least        one alcohol is chosen from monoalcohols comprising from 12 to 24        carbon atoms, or at least one alcohol is chosen from        monoalcohols comprising from 16 to 24 carbon atoms).

(n) the ETPEA has a softening point of greater than 70° C., for example,has a softening point of 70° C. to 190° C., or has a softening point of80° C. to 130° C., or has a softening point of 80° C. to 105° C.

(o) the composition has a hardness ranging from 20 g to 2000 g, forexample, has a hardness ranging from 20 g to 900 g, or has a hardnessranging from 20 g to 600 g.

As another example, the present invention also provides a compositioncomprising: (a) at least one liquid fatty phase comprising: (i) at leastone structuring polymer comprising a polyamide skeleton which comprisesat least one end group with at least one chain chosen from alkyl chainscomprising at least four carbon atoms and alkenyl chains comprising atleast four carbon atoms, bonded to the skeleton via at least one estergroup; and (ii) at least one amphiphilic compound which is liquid atroom temperature and which has an HLB value of less than 16, preferablyless than 8. This composition may be used, for example, to care for atleast one keratin material, or for treating at least one keratinmaterial, or may be present in a make-up composition for at least onekeratin material.

As another example, the present invention provides a mascara product, aneyeliner product, a foundation product, a lipstick product, a deodorantproduct, a make-up product for the body, a make-up-removing product, aneyeshadow product, a face powder product, a concealer product, atreating shampoo product, a hair conditioning product, an antisunproduct or a care product for the face or the body comprising: (a) atleast one liquid fatty phase comprising: (i) EPTEA; and (ii) at leastone amphiphilic compound which is liquid at room temperature and whichhas an HLB value of less than 16, preferably less than 8.

As another example, the present invention provides a structuredcomposition comprising a cosmetically acceptable medium and furthercomprising: (a) at least one liquid fatty phase comprising at least onestructuring polymer which comprises ETPEA; and (b) at least oneamphiphilic compound which is liquid at room temperature, with an HLBvalue of less than 16, preferably less than 8. Optionally, thecomposition is in cast form, and also optionally the composition is inthe form of a mascara product, an eyeliner product, a foundationproduct, a lipstick product, a deodorant product, a make-up product forthe body, a make-up-removing product, an eyeshadow product, a facepowder product, a concealer product, a treating shampoo product, a hairconditioning product, an antisun product or a care product for the faceor the body.

One or more of the following features may optionally be used tocharacterize the composition and/or components thereof: the compositionmay further comprise at least one dyestuff, where optionally: i) the atleast one dyestuff is chosen from lipophilic dyes, hydrophilic dyes,pigments and nacres, or ii) the at least one dyestuff is present in aconcentration ranging from 0.01% to 40% by weight relative to the totalweight of said composition, or the at least one dyestuff is present in aconcentration ranging from 5% to 25% by weight relative to the totalweight of said composition.

The present invention also provides a cosmetic process for caring for,making up or treating a keratin material comprising the application toat least one keratinous material of a cosmetic composition comprising:(a) at least one liquid fatty phase comprising: (i) at least onestructuring polymer comprising ETPEA; and (ii) at least one amphiphiliccompound which is liquid at room temperature and which has an HLB valueof less than 16, preferably less than 8.

The present invention also provides a process of structuring a liquidfatty phase in the form of a self-supporting solid comprising includingin said at least one liquid fatty phase a sufficient amount of (i) atleast one structuring polymer comprising ETPEA, and (ii) at least oneamphiphilic compound which is liquid at room temperature having an HLBvalue of less than 16, preferably less than 8; and wherein saidself-supporting solid is obtained. In optional embodiments, theself-supporting solid has a hardness ranging from 20 g to 2000 g, e.g.,has a hardness ranging from 20 g to 900 g, or has a hardness rangingfrom 20 g to 600 g.

The present invention also provides a process of structuring at leastone liquid fatty phase in the form of a glossy and/or non-migratingsolid comprising combining with said at least one liquid fatty phase asufficient amount of (i) at least one structuring polymer comprisingETPEA, and (ii) at least one amphiphilic compound which is liquid atroom temperature having an HLB value of less than 16, preferably lessthan 8; wherein said glossy and/or non-migrating solid is obtained.

The present invention also provides a process of structuring a cosmeticcomposition in the form of a physiologically acceptable compositionwhich is glossy and/or non-migrating comprising including in saidcomposition at least one liquid fatty phase, said at least one liquidfatty phase being structured with at least one structuring polymercomprising ETPEA and (ii) at least one amphiphilic compound having anHLB value of less than 16, preferably less than 8; wherein said glossyand/or non-migrating cosmetic composition is obtained.

The present invention also provides a process of making a cosmeticcomposition in the form of a physiologically acceptable compositionwhich is glossy and/or non-migrating comprising including in saidcomposition at least one liquid fatty phase, said at least one liquidfatty phase being structured with at least one structuring polymercomprising ETPEA and (ii) at least one amphiphilic compound having anHLB value of less than 16, preferably less than 8; wherein said glossyand/or non-migrating cosmetic composition is obtained.

In one aspect, the present invention provides a composition comprising,in a physiologically acceptable medium, at least one first polymer witha weight-average molecular mass of less than 100,000 (optionally lessthan 50,000, optionally less than 30,000, optionally 2,000-20,000,optionally 2,000-10,000) comprising ETPEA, and a dispersion of particlesof a second film-forming polymer that is insoluble in said medium.

The second film-forming polymer, which is different from the firstpolymer comprising EPTEA, is in the form of solid particles dispersed inthe physiologically acceptable medium. These particles may be dispersedin an aqueous phase or in a liquid fatty phase. The composition cancomprise a mixture of these second polymers. The second film-formingpolymer is insoluble in the medium of the composition, that is to saythat it remains in the form of particles in the mixture of theingredients of the composition forming the physiologically acceptablemedium. Thus, the expression “polymer that is insoluble in thephysiologically acceptable medium” should be understood as meaning apolymer whose solubility in this medium is less than 1% by weight. Thesecond film-forming polymer may be present in the composition accordingto the invention in a solids content ranging from 0.1% to 60% by weightrelative to the total weight of the composition, preferably from 0.5% to40% by weight and better still from 1% to 30% by weight. The expression“film-forming polymer” means a polymer, which is capable, by itself orin the presence of an auxiliary film-forming agent, of forming acontinuous and adherent film on a support, in particular on keratinmaterials. A film-forming polymer capable of forming a hydrophobic film,i.e., a polymer whose film has a water-solubility at 25° C. of less than1% by weight, is preferably used.

Among the film-forming polymers, which may be used in the composition ofthe present invention, mention may be made of synthetic polymers, ofradical-mediated type or of polycondensate type, and polymers of naturalorigin, and mixtures thereof. The expression “radical-mediatedfilm-forming polymer” means a polymer obtained by polymerization ofmonomers containing unsaturation, in particular ethylenic unsaturation,each monomer being capable of homopolymerizing (unlike polycondensates).The film-forming polymers of radical-mediated type may be, inparticular, vinyl polymers or copolymers, in particular acrylicpolymers. The vinyl film-forming polymers can result from thepolymerization of monomers containing ethylenic unsaturation andcontaining at least one acidic group and/or esters of these acidicmonomers and/or amides of these acidic monomers. Monomers bearing anacidic group that may be used include α,β-ethylenic unsaturatedcarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid,maleic acid or itaconic acid. (Meth)acrylic acid and crotonic acid arepreferably used, and more preferably (meth)acrylic acid. The esters ofacidic monomers are advantageously chosen from (meth)acrylic acid esters(also known as (meth)acrylates), especially (meth)acrylates of an alkyl,in particular of a C₁-C₃₀ and preferably C₁-C₂₀ alkyl, (meth)acrylatesof an aryl, in particular of a C₆-C₁₀ aryl, and (meth)acrylates of ahydroxyalkyl, in particular of a C₂-C₆ hydroxyalkyl. Among thealkyl(meth)acrylates which may be mentioned are methyl methacrylate,ethyl methacrylate, butyl methacrylate, isobutyl methacrylate,2-ethylhexyl methacrylate, lauryl methacrylate and cyclohexylmethacrylate. Among the hydroxyalkyl(meth)acrylates which may bementioned are hydroxyethyl acrylate, 2-hydroxypropyl acrylate,hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate. Among thearyl(meth)acrylates which may be mentioned are benzyl acrylate andphenyl acrylate. The (meth)acrylic acid esters that are particularlypreferred are the alkyl(meth)acrylates. The alkyl group of the estersmay be either fluorinated or perfluorinated, i.e., some or all of thehydrogen atoms of the alkyl group are substituted with fluorine atoms.As amides of the acidic monomers, mention may be made, for example, of(meth)acrylamides, and especially N-alkyl(meth)acrylamides, inparticular of a C₂-C₁₂ alkyl. Among the N-alkyl(meth)acrylamides whichmay be mentioned are N-ethylacrylamide, N-t-butylacrylamide,N-t-octylacrylamide and N-undecylacrylamide. The vinyl film-formingpolymers can also result from the homopolymerization or copolymerizationof monomers chosen from vinyl esters and styrene monomers. Inparticular, these monomers may be polymerized with acidic monomersand/or esters thereof and/or amides thereof, such as those mentionedabove. Examples of vinyl esters which may be mentioned are vinylacetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinylt-butylbenzoate. Styrene monomers which may be mentioned are styrene andα-methylstyrene. It is possible to use any monomer known to thoseskilled in the art which falls within the categories of acrylic andvinyl monomers (including monomers modified with a silicone chain).Among the film-forming polycondensates which may be mentioned arepolyurethanes, polyesters, polyesteramides, polyamides, epoxy esterresins and polyureas. The polyurethanes may be chosen from anionic,cationic, nonionic and amphoteric polyurethanes, polyurethane-acrylics,polyurethane-polyvinylpyrrolidones, polyester-polyurethanes,polyether-polyurethanes, polyureas and polyurea-polyurethanes, andmixtures thereof. The polyesters may be obtained, in a known manner, bypolycondensation of dicarboxylic acids with polyols, in particulardiols. The dicarboxylic acid may be aliphatic, alicyclic or aromatic.Examples of such acids which may be mentioned are: oxalic acid, malonicacid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid,pimelic acid, 2,2-dimethylglutaric acid, azelaic acid, suberic acid,sebacic acid, fumaric acid, maleic acid, itaconic acid, phthalic acid,dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid,1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid,2,5-norboranedicarboxylic acid, diglycolic acid, thiodipropionic acid,2,5-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid.These dicarboxylic acid monomers may be used alone or in combinationwith at least two dicarboxylic acid monomers. Among these monomers, theones preferably chosen are phthalic acid, isophthalic acid andterephthalic acid. The diol may be chosen from aliphatic, alicyclic andaromatic diols. The diol preferably used is one chosen from: ethyleneglycol, diethylene glycol, triethylene glycol, 1,3-propanediol,cyclohexanedimethanol, 4-butanediol. Other polyols which may be used areglycerol, pentaerythritol, sorbitol and trimethylolpropane. Thepolyesteramides may be obtained in a manner analogous to that of thepolyesters, by polycondensation of diacids with diamines or aminoalcohols. Diamines which may be used are ethylenediamine,hexamethylenediamine and meta- or para-phenylenediamine. An aminoalcoholwhich may be used is monoethanolamine. The polyester may also compriseat least one monomer bearing at least one group —SO₃M, with Mrepresenting a hydrogen atom, an ammonium ion NH₄+ or a metal ion suchas, for example, an Na+, Li+, K+, Mg²⁺, Ca²⁺, Cu²⁺, Fe²⁺ or Fe³⁺ ion. Adifunctional aromatic monomer comprising such a group —SO₃M may be usedin particular. The aromatic nucleus of the difunctional aromatic monomeralso bearing a group —SO₃M as described above may be chosen, forexample, from benzene, naphthalene, anthracene, biphenyl, oxybiphenyl,sulfonylbiphenyl and methylenebiphenyl nuclei. As examples ofdifunctional aromatic monomers also bearing a group —SO₃M, mention maybe made of: sulfoisophthalic acid, sulfoterephthalic acid, sulfophthalicacid, 4-sulfonaphthalene-2,7-dicarboxylic acid. The copolymerspreferably used are those based on isophthalate/sulfoisophthalate, andmore particularly copolymers obtained by condensation of diethyleneglycol, cyclohexanedimethanol, isophthalic acid and sulfoisophthalicacid. Such polymers are sold, for example, under the brand name EastmanAQ® by the company Eastman Chemical Products. The polymers of naturalorigin, optionally modified, may be chosen from shellac resin, sandaracgum, dammar resins, elemi gums, copal resins and cellulose polymers, andmixtures thereof.

According to a first embodiment of the composition according to theinvention, the second film-forming polymer may be present in the form ofparticles in dispersion in an aqueous phase, which is generally known asa latex or pseudolatex. The techniques for preparing these dispersionsare well known to those skilled in the art. Aqueous dispersions offilm-forming polymers which may be used are the acrylic dispersions soldunder the names Neocryl XK-90®, Neocryl A-1070®, Neocryl A-1090®,Neocryl BT-62®, Neocryl A-1079® and Neocryl A-523® by the companyAvecia-Neoresins; Dow Latex 432® by the company Dow Chemical; Daitosol5000 AD® by the company Daito Kasey Kogyo; or the aqueous dispersions ofpolyurethane sold under the names Neorez R-981® and Neorez R-974® by thecompany Avecia-Neoresins, Avalure UR-405®, Avalure UR-410®, AvalureUR-425®, Avalure UR-450®, Sancure 875®, Sancure 861®, Sancure 878® andSancure 2060® by the company Goodrich; Impranil 85® by the companyBayer; and Aquamere H-1511® by the company Hydromer. Aqueous dispersionsof film-forming polymers which may also be used are the polymerdispersions resulting from the radical-mediated polymerization of one ormore radical-mediated monomers within and/or partially at the surface ofpre-existing particles of at least one polymer chosen from the groupconsisting of polyurethanes, polyureas, polyesters, polyesteramidesand/or alkyds. These polymers are generally referred to as hybridpolymers.

One or more of the following features may optionally be used to describethe composition of the present invention:

(a) the first polymer is present in a content ranging from 0.01% to 10%by weight, relative to the total weight of the composition, preferablyranging from 0.05% to 5% by weight and better still ranging from 0.1% to3% by weight.

(b) the second film-forming polymer is chosen from the group formed byfree-radical polymers, polycondensates and -polymers of natural origin,and blends thereof.

(c) the second film-forming polymer is chosen from the group formed byvinyl polymers, polyurethanes, polyesters and cellulose polymers.

(d) the composition comprises an aqueous phase, optionally:

-   -   i) the aqueous phase comprises water and a water-miscible        organic solvent, where the water-miscible organic solvent is        optionally chosen from the group formed by lower monoalcohols        containing from 1 to 5 carbon atoms, glycols containing from 2        to 8 carbon atoms, C₃-C₄ ketones and C₂-C₄ aldehydes.    -   ii) the composition comprises a water-miscible organic solvent        chosen from the group ethanol, isopropanol, propylene glycol,        ethylene glycol, 1,3-butylene glycol and dipropylene glycol.    -   iii) the composition comprises water in a content ranging from        5% to 90% by weight relative to the total weight of the        composition.

(e) the second film-forming polymer is present in the form of particlesdispersed in an aqueous phase.

(f) the composition comprises an aqueous phase that comprises anadditional water-soluble film-forming polymer. Examples of water-solublefilm-forming polymers which may be mentioned are: proteins, for instanceproteins of plant origin such as wheat proteins and soybean proteins;proteins of animal origin such as keratins, for example keratinhydrolysates and sulfonic keratins; anionic, cationic, amphoteric ornonionic chitin or chitosan polymers; polymers of celluloses such ashydroxyethylcellulose, hydroxypropylcellulose, methylcellulose,ethylhydroxyethylcellulose and carboxymethylcellulose, and quaternizedcellulose derivatives; acrylic polymers or copolymers, such aspolyacrylates or polymethacrylates; vinyl polymers, for instancepolyvinylpyrrolidones, copolymers of methyl vinyl ether and of malicanhydride, the copolymer of vinyl acetate and of crotonic acid,copolymers of vinylpyrrolidone and of vinyl acetate; copolymers ofvinylpyrrolidone and of caprolactam; polyvinyl alcohol; polymers ofnatural origin, which are optionally modified, such as: (a) gum arabics,guar gum, xanthan derivatives, karaya gum; (b) alginates andcarrageenans; (c) glycoaminoglycans, hyaluronic acid and derivativesthereof; (d) shellac resin, sandarac gum, dammar resins, elemi gums andcopal resins; (e) deoxyribonucleic acid; (f) mucopolysaccharides such ashyaluronic acid and chondroitin sulfate, and mixtures thereof.

(g) the composition comprises a liquid fatty phase, where optionally

-   -   i) the liquid fatty phase comprises an oil chosen from the group        formed by oils of mineral, animal, plant or synthetic origin,        that are hydrocarbon-based, fluorinated and/or silicone-based,        alone or as a mixture.    -   ii) the composition comprises an oil that is volatile at room        temperature, optionally chosen from hydrocarbon-based volatile        oils containing from 8 to 16 carbon atoms, where the volatile        oil is optionally present in a content ranging from 0.1% to 98%        and preferably ranging from 1% to 65% by weight, relative to the        total weight of the composition.    -   iii) the liquid fatty phase is present in a content ranging from        2% to 98% by weight and preferably ranging from 5% to 85% by        weight, relative to the total weight of the composition.

(h) the second film-forming polymer is present in the form of particlesdispersed in a liquid fatty phase and surface-stabilized, whereoptionally:

-   -   i) the polymer particles are stabilized with a stabilizer chosen        from block polymers, grafted polymers and random polymers, and        blends thereof.    -   ii) the stabilizer is a grafted-block or block polymer,        comprising at least one block resulting from the polymerization        of ethylenic monomers comprising one or more optionally        conjugated ethylenic bonds, and at least one block of a styrene        polymer.

(i) the second film-forming polymer is present in a content ranging from0.1% to 60% by weight and preferably from 10% to 45% by weight, relativeto the total weight of the composition.

(j) the size of the particles of the second film-forming polymer rangesfrom 5 nm to 600 nm and preferably from 20 nm to 300 nm.

(k) the composition comprises at least one wax, where optionally:

-   -   i) at least one wax has a melting point of greater than 30° C.,        and less than about 120° C.; and/or    -   ii) the wax is chosen from the group formed by beeswax, lanolin        wax, Chinese insect waxes, rice wax, carnauba wax, candelilla        wax, ouricury wax, cork fiber wax, sugar cane wax, Japan wax,        sumach wax, montan wax, microcrystalline waxes, paraffin waxes,        ozokerites, ceresin wax, lignite wax, polyethylene waxes and the        waxes obtained by Fisher-Tropsch synthesis, fatty acid esters of        glycerides that are solid at 40° C., waxes obtained by catalytic        hydrogenation of animal or plant oils containing linear or        branched C₈-C₃₂ fatty chains, silicone waxes and fluoro waxes,        and mixtures thereof; and/or    -   iii) the wax is present in a content ranging from 0.1% to 50% by        weight, relative to the total weight of the composition,        preferably from 0.5% to 30% by weight and better still from 1%        to 20% by weight.

(l) the composition comprises at least one dyestuff, for example, adyestuff chosen from pigments, nacres, liposoluble dyes andwater-soluble dyes, and mixtures thereof. Optionally, the dyestuff ispresent in a proportion of from 0.01% to 50% relative to the totalweight of the composition, preferably ranging from 0.01% to 30% byweight.

(m) The composition is formulated as a personal care composition ormake-up composition for keratin materials.

(n) The composition comprises at least one additive chosen fromantioxidants, fillers, preserving agents, fragrances, neutralizingagents, thickeners and cosmetic or dermatological active agents, andmixtures thereof.

(o) The composition is formulated as a mascara, an eyeliner, a productfor the eyebrows, a product for the lips, a face powder, an eyeshadow, afoundation, a make-up product for the body, a concealer product, a nailvarnish, a skincare product or a hair care product.

(p) These compositions of the present invention may be used for themaking up or caring for the keratin materials of human beings. Forinstance, they may be used to obtain a deposit which adheres to keratinmaterials and/or a quick make-up result on keratin materials. Whenformulated as a mascara, the composition may thicken quickly whenapplied to eyelashes, and/or may be used to lengthen the eyelashes.

In one aspect, the present invention provides a colored transparent ortranslucent cosmetic compositions exhibiting a turbidity of less than800 NTU and comprising, in a transparent or translucent cosmetic base,an amount of less than 0.5% by weight, with respect to the finalcosmetic composition, of at least one colored pigment which is insolublein the cosmetic base and which has a mean particle size of greater than100 nm. Optionally, one or more of the following criteria may be used tocharacterize these compositions of the present invention:

(a) the composition contains pigment or pigments having a meanparticle-size of greater than 200 nm; and/or

(b) the composition contains pigment and the concentration of thecolored pigment or pigments is less than 0.01% by weight with respect tothe final cosmetic composition, optionally the concentration of thecolored pigment or pigments is at most equal to 0.001% by weight withrespect to the final cosmetic composition; and/or

(c) the composition exhibits a turbidity of less than 500 NTU.

(d) the transparent or translucent cosmetic base is chosen from aqueousor oily gels, in particular in the form of sticks.

(e) the transparent or translucent cosmetic base is an anhydrouslipophilic cosmetic base.

(f) the transparent or translucent cosmetic base is an anhydrous gelformed of a fatty phase which is liquid at ambient temperaturecomprising polar and/or nonpolar oils, which fatty phase is structuredby a gelling agent for fatty phases comprising ETPEA and optionally oneor more other gellants chosen from hydrophobic pyrogenic silicas,gelling polyamides, hydrophobic galactomannans, and their mixtures.

(g) the composition additionally comprises physiologically acceptableadditives chosen from dispersing agents, fragrances, sunscreen agents,preservatives, antioxidants and cosmetic active principles.

In one aspect, the present invention provides a structured nail polishcomposition comprising at least one liquid organic phase comprising atleast one volatile organic solvent, the liquid organic phase beingstructured by at least one first polymer comprising ETPEA. The ETPEApreferably has a weight-average molecular mass of less than or equal to100 000. In a related aspect, the present invention provides a sticknail polish composition comprising at least one liquid organic phasecomprising at least one volatile organic solvent, the liquid organicphase being structured by at least one first polymer comprising ETPEA.The ETPEA preferably has a weight-average molecular mass of less than orequal to 100 000. In a related aspect, the present invention provides acosmetic composition comprising an organic phase, a first polymercomprising ETPEA and a second additional film-forming polymer, theorganic phase comprising at least one volatile organic solvent or amixture of volatile organic solvents exhibiting mean Hansen solubilityparameters dD, dP and dH at 25° C. which satisfy the followingconditions: 15 (J/cm³)^(1/2)≦dD≦19 (J/cm³)^(1/2); dP≦10 (J/cm³)^(1/2);dH≦10 (J/cm³)^(1/2). In a related aspect, the present invention providesa nail polish composition comprising a liquid organic phase, a firstpolymer comprising ETPEA and a second additional film-forming polymer,the organic phase comprising at least one volatile organic solvent or amixture of volatile organic solvents exhibiting mean Hansen solubilityparameters dD, dP and dH at 25° C. which satisfy the followingconditions: 15 (J/cm³)^(1/2)≦dD≦19 (J/cm³)^(1/2); dP≦10 (J/cm³)^(1/2);dH≦10 (J/cm³)^(1/2). Optionally, in each of these four aspects, thecomposition or a component thereof may be further characterized ordefined by reference to one or more of the following criteria:

(a) the volatile organic solvent is chosen from volatile organicsolvents or mixtures of volatile organic solvents exhibiting mean Hansensolubility parameters dD, dP and dH at 25° C. which satisfy thefollowing conditions: 15 (J/cm³)^(1/2)≦dD≦19 (J/cm³)^(1/2); dP≦10(J/cm³)^(1/2); dH<10 (J/cm³)^(1/2).

(b) dP≦5 (J/cm³)^(1/2).

(c) dH≦9 (J/cm³)^(1/2).

(d) The square root of (4(17-dD)²+dP²+dH²)) is less than L, where L isequal to 10 (J/cm³)^(1/2) and better still L is 9 (J/cm³)^(1/2).

(e) The volatile organic solvent is chosen from the group formed byesters having from 4 to 8 carbon atoms and alkanes having from 6 to 10carbon atoms.

(f). The volatile organic solvent is chosen from the group formed byethyl acetate, n-propyl acetate, isobutyl acetate, n-butyl acetate andheptane.

(g) The volatile organic solvent is chosen from branched C8-C16 alkanes,branched C8-C16 esters and mixtures thereof.

(h) The volatile organic solvent is chosen from C8-C16 isoparaffins,isododecane and their mixtures.

(i) The volatile organic solvent is present in a content ranging from20% to 98% by weight with respect to the total weight of thecomposition, preferably from 30% to 90% by weight and better still from40% to 85% by weight.

(j) The liquid organic phase additionally comprises at least onenonvolatile oil.

(k) The liquid organic phase represents from 5 to 99% of the totalweight of the composition, preferably from 20 to 75%.

(l) The composition further comprises a second film-forming polymer,where optionally:

-   -   i) the second film-forming polymer is chosen from the group        formed by cellulose polymers, polyurethanes, acrylic polymers,        vinyl polymers, polyvinylbutyrals, alkyd resins, resins        resulting from aldehyde condensation products, and        arylsulfonamide-epoxy resins; and/or    -   ii) the second film-forming polymer is present in a content        ranging from 0.1% to 60% by weight with respect to the total        weight of the composition, preferably ranging from 2% to 40% by        weight and better still from 5% to 25% by weight.

(m) The composition further comprises at least one additive chosen fromcoloring materials, antioxidants, preservatives, fragrances, fillers,waxes, neutralizing agents, cosmetic or dermatological activeprinciples, dispersing agents, spreading agents, sunscreens, and theirmixtures.

(n) The composition is provided in the form of a stiff gel and inparticular of an anhydrous stick.

(o) The composition has a hardness ranging from 30 to 300 g, measured bythe “cheesewire” method described herein.

In one aspect, the present invention provides a composition, preferablya transfer resistant composition, which may also be pliable andcomfortable to wear upon application to skin or other substrate. Thecompositions comprise at least one structuring polymer including ETPEAand at least one film-forming silicone resin. The compositions areoptionally anhydrous.

Optional components of the compositions include, without limitation, atleast one liquid fatty phase, the phase optionally comprising an oil(e.g., a polar oil, an apolar oil) having affinity for the ETPEA,non-volatile oil, silicone oil, a second fatty material (e.g., gum,fatty materials pasty), fatty alcohol (e.g., myristyl alcohol, cetylalcohol, stearyl alcohol, behenyl alcohol), oil-soluble polymer (e.g.,alkylated guar gum, alkyl cellulose), oil-soluble cationic surfactant(e.g., quaternary ammonium compounds, fatty amines, salts of fattyamines), wax (e.g., carnauba wax, candelilla wax, ouricury wax,microcrystalline waxes, lanolin wax, silicon wax, jojoba oil, etc.),fatty acid (e.g., oleic acid, linoleic acid, linolenic acid),siloxysilicate, and silsesquioxanes.

In one aspect the present invention provides compositions and methodswherein ETPEA is present in a make-up composition comprising aphysiologically acceptable medium containing a fatty phase, as an agentfor increasing the speed of achieving a make-up result on keratinmaterials and/or for increasing the adhesion to said keratin materialsand/or for rapidly increasing the amount of make-up deposited on thekeratin materials. In a related aspect, the present invention providescompositions and methods wherein ETPEA is present in a composition forexpress make-up and/or with good adhesion to and/or that loads quicklyonto keratin materials, said composition comprising a physiologicallyacceptable medium containing a fatty phase. Optionally, one or more ofthe following criteria may further define these compositions andmethods:

(a) the fatty phase contains at least one wax, e.g., a wax chosen fromthe group formed by beeswax, lanolin wax, Chinese insect waxes, ricewax, carnauba wax, candelilla wax, ouricury wax, cork fiber wax, sugarcane wax, Japan wax, sumach wax, montan wax, microcrystalline waxes,paraffin waxes, ozokerites, ceresin wax, lignite wax, polyethylene waxesand the waxes obtained by Fisher-Tropsch synthesis, fatty acid estersand glycerides that are solid at 40° C., the waxes obtained by catalytichydrogenation of animal or plant oils containing linear or branchedC8-C32 fatty chains, silicone waxes and fluoro waxes, and mixturesthereof, where the wax is optionally present in a content ranging from0.1% to 50% by weight, relative to the total weight of the composition,preferably from 0.5% to 30% by weight and better still from 1% to 20% byweight.

(b) the fatty phase comprises at least one oil, e.g., an oil chosen fromthe group formed by oils of mineral, animal, plant or synthetic origin,that are hydrocarbon-based, fluorinated and/or silicone-based, alone oras a mixture. The oil is optionally a volatile oil, e.g., a volatile oilchosen from hydrocarbon-based volatile oils containing from 8 to 16carbon atoms, where the volatile oil is optionally present in a contentranging from 0.1% to 98% by weight and preferably ranging from 1% to 65%by weight, relative to the total weight of the composition.

(c) the composition comprises an aqueous phase containing water or amixture comprising water and a water-miscible organic solvent.

(d) The composition comprises a second film-forming polymer that isdifferent than the first polymer. The second film-forming polymer may bechosen from the group formed by vinyl polymers, polyurethanes,polyesters, polyamides, polyureas and cellulose polymers. Optionally,the second film-forming polymer is present in a solids content rangingfrom 0.1% to 60% by weight, preferably from 0.5% to 40% by weight andbetter still from 1% to 30% by weight, relative to the total weight ofthe composition.

(e) The composition contains at least one dyestuff, e.g., a dyestuffchosen from pigments, nacres, water-soluble dyes and liposoluble dyes,and mixtures thereof, where optionally the dyestuff is present in aproportion of from 0.01% to 50% relative to the total weight of thecomposition, preferably ranging from 0.01% to 30% by weight.

(f) The composition contains at least one additive chosen fromsurfactants, thickeners, antioxidants, fillers, preserving agents,fragrances, neutralizing agents and cosmetic or dermatological activeagents, and mixtures thereof.

(g) The composition is in the form of a mascara, an eyeliner, a productfor the eyebrows, a product for the lips, a face powder, an eyeshadow, afoundation, a make-up product for the body, a concealer product, a nailvarnish or a hair care product.

The compositions of the present invention may contain one or more apolaroils, where representative apolar oils according to the presentinvention may be chosen from silicone oils such as volatile andnonvolatile, linear, branched and cyclic polydimethylsiloxanes (PDMSs)that are liquid at room temperature; polydimethylsiloxanes comprisinggroups chosen from alkyl groups, alkoxy groups and phenyl groups,optionally pendant or terminal, and each comprising from 2 to 24 carbonatoms; phenylsilicones such as phenyl trimethicones, phenyldimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyldimethicones, diphenyl methyldiphenyl trisiloxanes and 2-phenylethyltrimethylsiloxysilicates; linear, branched and cyclic, volatile andnonvolatile hydrocarbons and fluorocarbons of synthetic and mineralorigin, such as volatile liquid paraffins (such as isoparaffins andisododecane), nonvolatile liquid paraffins and derivatives thereof,petroleum jelly, polydecenes, hydrogenated polyisobutene such asparleam, and squalane. In one embodiment, the apolar oil is chosen fromthose of the hydrocarbon-based type chosen from mineral and syntheticorigin. In another embodiment, the apolar oil is chosen from parleamoil, isoparaffins, squalane and mixtures thereof.

The compositions of the present invention may contain one or more polaroils. For example, it may be possible to add polar oils to the apolaroils, the apolar oils acting in particular as co-solvent for the polaroils. Representative polar oils of the present invention may be chosenfrom: hydrocarbon-based plant oils having a high content oftriglycerides chosen from fatty acid esters of glycerol in which thefatty acids may have varied chain lengths, these chains may be chosenfrom linear, branched, cyclic, saturated and unsaturated chains.Non-limiting examples of these oils are wheat germ oil, corn oil,sunflower oil, karite butter, castor oil, sweet almond oil, macadamiaoil, apricot oil, soybean oil, rape seed oil, cotton oil, alfalfa oil,poppy oil, pumpkin oil, sesame oil, marrow oil, avocado oil, hazelnutoil, grape seed oil, blackcurrant seed oil, evening primrose oil, milletoil, barley oil, quinoa oil, olive oil, rye oil, safflower oil,candlenut oil, passion flower oil, musk rose oil and caprylic/capricacid triglycerides such as those sold by Stearineries Dubois Co. andthose sold under the names Miglyol 810, 812 and 818 by Dynamit Nobel Co.

The compositions of the present invention may contain one or moresynthetic oils and esters of formula R₁COOR₂ in which R₁ is chosen fromlinear and branched higher fatty acid groups comprising from 1 to 40carbon atoms, such as from 7 to 19 carbon atoms; and R₂ is chosen frombranched hydrocarbon-based groups comprising from 1 to 40 carbon atoms,such as from 3 to 20 carbon atoms, with the proviso that the totalnumber of carbon atoms in R₁ and R₂ is greater than or equal to 10, suchas, for example, in purcellin oil (cetostearyl octanoate), isononylisononanoate, C.sub.12-C.sub.15 alkyl benzoates, isopropyl myristate,2-ethylhexyl palmitate, alkyl octanoates, polyalkyl octanoates,decanoates ricinoleates, hydroxylated esters such as isostearyl lactateand diisostearyl malate, and pentaerythritol esters. Optionally, thesynthetic ethers comprise from 10 to 40 carbon atoms.

A composition of the present invention may contain emulsifyingsurfactants. Such surfactants make it possible to obtain an oil-in-wateror wax-in-water emulsion. The specific type and amount of such asurfactant may be selected according to routine skill in the art.Typically the surfactant is present in a proportion ranging from 2% to30% by weight relative to the total weight of the composition, andbetter still from 5% to 15%. These surfactants may be chosen from, e.g.,anionic and nonionic surfactants. Reference may be made to “Encyclopediaof Chemical Technology, Kirk-Othmer”, volume 22, pp. 333-432, 3rdedition, 1979, Wiley, for the definition of the properties and functions(emulsifying) of surfactants, in particular pp. 347-377 of saidreference, for the anionic and nonionic surfactants. Exemplarysurfactants include, without limitation:

nonionic surfactants: fatty acids, fatty alcohols, polyethoxylated orpolyglycerolated fatty alcohols such as polyethoxylated stearyl orcetylstearyl alcohol, fatty acid esters of sucrose, alkylglucose esters,in particular polyoxyethylenated fatty esters of C.sub.1-C.sub.6 alkylglucose, and mixtures thereof.

anionic surfactants: C₁₆-C₃₀ fatty acids neutralized with amines,aqueous ammonia or alkaline salts, and mixtures thereof.

The compositions of the present invention may include a stabilizer,where the stabilizer is useful to, e.g., stabilize polymer particles.Exemplary stabilizers are block polymers, grafted polymers and/or arandom polymers, which may be used alone or as a mixture. Dispersions offilm-forming polymer in the liquid fatty phase, in the presence ofstabilizers, are disclosed in particular in documents EP-A-0 749 746,EP-A-0 923 928 and EP-A-0 930 060, the content of which is incorporatedin the present patent application by reference. Among the graftedpolymers that may be mentioned are silicone polymers grafted with ahydrocarbon-based chain; hydrocarbon-based polymers grafted with asilicone chain. Grafted copolymers having, for example, an insolubleskeleton of polyacrylic type with soluble grafts ofpoly(12-hydroxystearic acid) type are also suitable. Grafted-block orblock copolymers comprising at least one block of polyorganosiloxanetype and at least one block of a free-radical polymer may also be used,for instance grafted copolymers of acrylic/silicone type which may beused especially when the non-aqueous medium is silicone-based. Thestabilizer may also be chosen from grafted-block or block copolymerscomprising at least one block of polyorganosiloxane type and at leastone block of a polyether. The polyorganosiloxane block may especially bea polydimethylsiloxane or a poly(C2-C18)alkylmethylsiloxane; thepolyether block may be a C2-C18 polyalkylene, in particularpolyoxyethylene and/or polyoxypropylene. In particular, dimethiconecopolyols or (C2-C18)alkylmethicone copolyols may be used. It ispossible, for example, to use the dimethicone copolyol sold under thename “Dow Corning 3225C” by the company Dow Corning, or the laurylmethicone copolyol sold under the name “Dow Corning Q2-5200” by thecompany Dow Corning. As grafted-block or block copolymers, use may bemade of copolymers comprising at least one block resulting from thepolymerization of at least one ethylenic monomer, containing one or moreoptionally conjugated ethylenic bonds, such as ethylene, butadiene orisoprene, and at least one block of a styrene polymer. When theethylenic monomer comprises several optionally conjugated ethylenicbonds, the residual ethylenic unsaturations after the polymerization aregenerally hydrogenated. Thus, in a known manner, the polymerization ofisoprene leads, after hydrogenation, to the formation ofethylene-propylene block, and the polymerization of butadiene leads,after hydrogenation, to the formation of ethylene-butylene block. Amongthese block copolymers, mention may be made of copolymers of “diblock”or “triblock” type, of the type such as polystyrene/polyisoprene,polystyrene/polybutadiene such as those sold under the name “LuvitolHSB” by BASF, of the polystyrene/copoly(ethylene-propylene) type such asthose sold under the name “Kraton” by Shell Chemical Co., oralternatively of the polystyrene/copoly(ethylene-butylene) type. Asgrafted-block or block copolymers comprising at least one blockresulting from the polymerization of at least one ethylenic monomer,such as ethylene or isobutylene, and of at least one block of an acrylicpolymer such as methyl methacrylate, mention may be made of thepoly(methyl methacrylate)/polyisobutylene diblock or triblock copolymersor the grafted copolymers containing a poly(methyl methacrylate)skeleton and polyisobutylene grafts. As grafted-block or blockcopolymers comprising at least one block resulting from thepolymerization of at least one ethylenic monomer and of at least oneblock of a polyether such as a C2-C18 polyoxyalkylene, in particularpolyoxyethylene and/or polyoxypropylene, mention may be made ofpolyoxyethylene/polybutadiene or polyoxyethylene/polyisobutylene diblockor triblock copolymers. Use may also be made of copolymers of C1-C4alkyl(meth)acrylates, and of C8-C30 alkyl(meth)acrylates. Mention may bemade in particular of the stearyl methacrylate/methyl methacrylatecopolymer. When the compositions of the invention include a liquid fattyphase, and silicon oil is present in that phase, the stabilizer ispreferably chosen from the group: consisting of grafted-block or blockcopolymers comprising at least one block of polyorganosiloxane type andat least one block of a free-radical polymer or of a polyether or of apolyester, for instance polyoxy(C2-C18)alkylene blocks and especiallypolyoxypropylene and/or oxyethylene blocks. When the liquid fatty phasedoes not comprise a silicone oil, the stabilizer is preferably chosenfrom the group consisting of: (a) grafted-block or block copolymerscomprising at least one block of polyorganosiloxane type and at leastone block of a free-radical polymer or of a polyether or of a polyester,(b) copolymers of C1-C4 alkyl acrylates or methacrylates and of C8-C30alkyl acrylates or methacrylates, (c) grafted-block or block copolymerscomprising at least one block resulting from the polymerization of atleast one ethylenic monomer containing conjugated ethylenic bonds, andat least one block of a vinyl or acrylic polymer or of a polyether or ofa polyester, or blends thereof. Diblock polymers may be used as astabilizer.

The compositions of the present invention may contain one or morepigments. The pigments may be chosen from organic, inorganic orcomposite pigments. Exemplary inorganic pigments include iron oxides,chromium oxide, chromium hydrate, ultramarines (polysulfides of aluminumsilicates), cobalt blue, Prussian blue (ferric ferrocyanide), manganeseviolet, manganese pyrophosphate and metal powders, such as silver oraluminum powders. Exemplary organic pigments include carbon black,thioindigo and flaming red. Exemplary composite pigments include lakesor salts formed from calcium, barium, aluminum, strontium, zirconium andtheir mixtures and from organic acid dyes immobilized on an organic orinorganic support, where exemplary lakes include the calcium salt oflithol red B on rosin and barium sulfate (D&C Red No. 7 calcium lake),the aluminum salt of tartrazine on alumina (FD&C Yellow No. 5 aluminumlake), the aluminum salt of eosin on alumina and titanium dioxide (D&CRed No. 21 aluminum lake), the aluminum salt of phloxin B on alumina(D&C Red No. 27 aluminum lake), the aluminum salt of brilliant yellowFCF on alumina (FD&C Yellow No. 6 aluminum lake) and the aluminum saltof brilliant blue on alumina (FD&C Blue No. 1 aluminum lake). Exemplarywhite pigments include titanium dioxide, zirconium dioxide, ceriumdioxide and zinc oxide. The pigment may be coated with materials chosenfrom silicones, amino acids and fluorinated compounds.

In one aspect, the coloring material according to the invention can bechosen from lipophilic dyes, pigments and pearlescent agents commonlyused in cosmetic or dermatological compositions, and their mixtures. Thecoloring material is generally present in a proportion of 0.01 to 10% ofthe total weight of the composition, preferably of 0.1 to 8%, if it ispresent. Fat-soluble dyes are, for example, Sudan red, DC Red 17, DCGreen 6, beta-carotene, soybean oil, Sudan brown, DC Yellow 11, DCViolet 2, DC Orange 5 or quinoline yellow. They can typically representfrom 0.1 to 10% of the weight of the compositions and better still from0.1 to 6%. The pigments can be white or colored, inorganic and/ororganic and coated or uncoated. Mention may be made, among inorganicpigments, of titanium dioxide, which is optionally surface treated,zirconium or cerium oxides and iron or chromium oxides, manganeseviolet, ultramarine blue, chromium hydrate and ferric blue. Mention maybe made, among organic pigments, of carbon black, pigments of D & C typeand lakes based on cochineal carmine or on barium, strontium, calcium oraluminum. The pigments can typically represent from 0.1 to 50% andbetter still from 2 to 30% of the total weight of the composition, ifthey are present. The pearlescent pigments can be chosen from whitepearlescent pigments, such as mica covered with titanium oxide or withbismuth oxychloride, colored pearlescent pigments, such as titaniumoxide-coated mica with iron oxides, titanium oxide-coated mica with inparticular ferric blue or chromium oxide, or titanium oxide-coated micawith an organic pigment of the abovementioned type, and pearlescentpigments based on bismuth oxychloride. They can typically represent from0.1 to 20% of the total weight of the composition and better still from0.1 to 15%, if they are present.

The compositions of the invention may contain a liquid organic phasethat comprises at least one volatile organic solvent or a mixture ofvolatile organic solvents (within the meaning of the final mixture)exhibiting mean Hansen solubility parameters dD, dP and dH at 25° C.which satisfy the following conditions: 15 (J/cm³)^(1/2)≦dD≦19(J/cm³)^(1/2); dP≦10 (J/cm³)^(1/2); and dH<10 (J/cm³)^(1/2). Thedefinition of the solvents in the three-dimensional solubility spaceaccording to Hansen is described in the article by C. M. Hansen: “Thethree-dimensional solubility parameters”, J. Paint Technol., 39, 105(1967): dD characterizes the London dispersion forces resulting from theformation of dipoles induced during molecular impacts; dP characterizesthe forces of Debye interaction between permanent dipoles and the forcesof Keesom interactions between induced dipoles and permanent dipoles; dHcharacterizes the forces of specific interactions (hydrogen bond,acid/base or donor/acceptor type and the like). The parameters dD, dPand dH are expressed in (J/cm³)^(1/2).

Suitable volatile organic solvent which may be used in the invention areselected from volatile hydrocarbonaceous oils having from 4 to 16 carbonatoms and their mixtures and in particular linear C6-C10 alkanes, suchas n-hexane, n-heptane or n-octane, branched C8-C16 alkanes, C8-C16isoalkanes (also known as isoparaffins), isododecane, isodecane,isohexadecane and, for example, the oils sold under the tradenames ofIsopars or Permethyls, esters having from 4 to 8 carbon atoms, such asethyl acetate, n-propyl acetate, isobutyl acetate or n-butyl acetate,branched C8-C16 esters, such as isohexyl neopentanoate, and theirmixtures. The volatile organic solvent may be chosen from volatilehydrocarbonaceous oils having from 4 to 10 carbon atoms and theirmixtures.

Mention may also be made, as to other volatile organic solvents whichcan be used in the invention, of linear or cyclic silicone oils having aviscosity at ambient temperature of less than 8 centistokes (8 10⁻⁶ m²s)and having in particular from 2 to 7 silicon atoms, these siliconesoptionally comprising alkyl or alkoxy groups having from 1 to 10 carbonatoms. Mention may in particular be made, as volatile silicone oil whichcan be used in the invention, of octamethylcyclotetrasiloxane,decamethylcyclo-pentasiloxane, dodecamethylcyclohexasiloxane,heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane,hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane,dodecamethylpentasiloxane and their mixtures.

Other suitable volatile organic solvents include volatile fluorinatedsolvents.

A component of the compositions of the invention may be a polymer addedspecifically for its film-forming ability. The film-forming polymer canbe chosen from cellulose polymers, such as nitrocellulose, celluloseacetate, cellulose acetate butyrate, cellulose acetate propionate orethyl cellulose, or alternatively polyurethanes, acrylic polymers, vinylpolymers, polyvinylbutyrals, alkyd resins, resins resulting fromaldehyde condensation products, such as aryl-sulfonamide-formaldehyderesins, for example toluene-sulfonamide-formaldehyde resin, orarylsulfonamide-epoxy resins. For example, the film-forming polymer maybe nitrocellulose RS ⅛ sec.; RS ¼ sec.; ½ sec.; RS 5 sec.; RS 15 sec.;RS 35 sec.; RS 75 sec.; RS 150 sec.; AS ¼ sec.; AS ½ sec.; SS ¼ sec.; SS½ sec.; SS 5 sec.; sold in particular by Hercules;toluenesulfonamide-formaldehyde resin “Ketjentflex MS80” from Akzo or“Santolite MHP” or “Santolite MS80” from Faconnier or “Resimpol 80” fromPan Americana, alkyd resin “Beckosol ODE 230-70-E” from Dainippon,acrylic resin “Acryloid B66” from Rohm & Haas, or polyurethane resin“Trixene PR 4127” from Baxenden. When present, the film-forming polymercan be present in the composition according to the invention in acontent ranging from about 0.1% to 60% by weight with respect to thetotal weight of the composition, preferably ranging from about 2% to 40%by weight and better still from about 5% to 25% by weight.

In one aspect, the ETPEA-containing composition of the inventioncontains at least one inert filler. The term “filler” means any particlethat is solid at room temperature and atmospheric pressure, used aloneor in combination, which does not react chemically with the variousingredients of the composition and which is insoluble in theseingredients, even when these ingredients are raised to a temperatureabove room temperature and in particular to their softening point ortheir melting point.

The at least one inert filler has a melting point at least greater than150° C., for example greater than 170° C. and further as for example,greater than 200° C. The at least one inert filler may or may not beabsorbent, i.e., capable in particular of absorbing the oils of thecomposition and also the biological substances secreted by the skin. Theabsorbent fillers often have the property of making the deposit ofcomposition on the keratin materials matte, which is particularlydesired for a foundation and a concealer product. In one embodiment, theat least one inert filler may have an apparent diameter ranging from0.01 μm to 150 μm, such as from 0.5 μm to 120 μm, for example from 1 μmto 80 μm. An apparent diameter corresponds to the diameter of the circleinto which the elementary particle fits along its shortest dimension(thickness for leaflets).

The at least one inert filler may be present in the inventivecomposition in an amount ranging from 0.1% to 40% relative to the weightof the total composition, such as from 2% to 30%, and, for example, from5% to 20%.

The at least one inert filler may be mineral or organic, and lamellar,spherical or oblong. The at least one inert filler may be chosen fromtalc, mica, silica, kaolin, polyamide powders such as Nylon® (Orgasol®from Atochem) powder, poly-β-alanine powder, polyethylene powder,acrylic polymer powder and in particular polymethyl methacrylate (PMMA)powder, for instance the product sold or made by Wacker under thereference Covabead LH-85 (particle size 10-12 μm) or acrylic acidcopolymer powder (Polytrap® from Dow Corning), polytetrafluoroethylene(Teflon®) powders, lauroyllysine, boron nitride, starch, hollow polymermicrospheres such as those of polyvinylidene chloride/acrylonitrile, forinstance Expancel® (Nobel Industrie), hollow polymer microspheres(Tospearl® from Toshiba, for example), precipitated calcium carbonate,magnesium carbonate and hydrocarbonate, hydroxyapetite, hollow silicamicrospheres (Silica Beads® from Maprecos), glass or ceramicmicrocapsules and polyester particles. The at least one inert filler maybe surface-treated, e.g., to make them lipophilic.

The at least one inert filler may be porous so as to absorb the sweatand/or sebum secreted by the skin. Such inert fillers include silica,polyethylene powder, polyamide (Nylon®) powder, kaolin, starchderivatives and Polytrap®.

In order to minimize the exudation of the composition in cast form, theat least one inert filler used in the composition may contain a chemicalgroup of the same chemical nature as those of the units of thestructuring polymer or a chemical group capable of forming physicalbonds of the same type as that of the units of the polymer (for example,chosen from self-complementary hydrogen bonds, π interactions betweenunsaturated rings or filler-transfer interactions, dipolar interactions,and coordination bonds with organometallic derivatives). Thus, forstructuring polymers containing units of the amide, urea and/or urethanetype, the at least one inert filler used may contain groups capable offorming hydrogen bonds, like these structuring polymers. As fillerscapable of forming hydrogen bonds, mention may be made of fillers orparticles of acrylic polymer such as PMMA for instance the product soldby Wacker under the reference Covabead LH-85 (particle size 10-12 μm)and Polytrap® sold, or made by Dow Corning, hydrophobic-treated silica,polyamide (Nylon®) powders (Orgasol® from Atochem), and mixturesthereof. For units of the ester type, the fillers used may be of thepolyester type.

The surface of the silica may be chemically modified, by hydrophobicchemical treatments, giving rise to a decrease in the,number of silanolgroups. The hydrophobic groups may be:

-   -   trimethylsiloxyl groups, which are obtained, for example, by        treating fumed silica in the presence of hexamethyldisilazane.        Silicas thus treated are known as “silica silylate” according to        the CTFA (6th edition, 1995). They are sold, or made for        example, under the references “Aerosil R812®” by the company        Degussa and “CAB-O-SIL TS-530®” by the company Cabot;    -   dimethylsilyloxyl or polydimethylsiloxane groups, which are        obtained, for example, by treating fumed silica in the presence        of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus        treated are known as “silica dimethyl silylate” according to the        CTFA (6th edition, 1995). They are made or sold, for example,        under the references “Aerosil R972®” and “Aerosil R974®” by the        company Degussa, and “CAB-O-SIL TS-610®” and “CAB-O-SIL TS-720®”        by the company Cabot;    -   groups derived from reacting fumed silica with silane alkoxides        or siloxanes. These treated silicas are, for example, the        products made or sold under the reference “Aerosil R805®” by the        company Degussa.

According to the invention, a hydrophobic silica, such as a fumedsilica, may be used as lipophilic gelling agent or rheological agent.The use of fumed silica may make it possible to obtain a translucent oreven transparent composition, in particular in the form of a stick whichdoes not exude, in the absence of opacifying particles such as waxes,fillers and pigments (including nacres). In one embodiment, the filleris lipophilic or treated to be lipophilic.

In one aspect, a composition according to the present invention maycontain at least one fatty compound that is pasty or viscous at roomtemperature. For the purposes of the invention, the expression “pastyfatty substance” means a fatty substance with a melting point rangingfrom 20° C. to 55° C., for example from 25° C. to 45° C., and from 25°C. to 40° C., and/or a viscosity at 40° C. ranging from 0.1 to 40 Pa·s(1 to 400 poises), for example from 0.5 to 25 Pa·s, measured using aContraves TV or Rheomat 80 viscometer, equipped with a spindle rotatingat 240 min⁻¹ for supplying with 60 Hz or at 200 min⁻¹ for supplying with50 Hz. A person skilled in the art can select the spindle for measuringthe viscosity from the spindles MS-r3 and MS-r4, on the basis of hisgeneral knowledge, so as to be able to carry out the measurement of thepasty compound tested.

According to the invention, at least one pasty fatty substance can beused. The at least one pasty fatty substance may be chosen fromhydrocarbon-based compounds, optionally of polymeric type; it can alsobe chosen from silicone compounds and/or fluoro compounds; it may alsobe in the form of a mixture of hydrocarbon-based compounds and/orsilicone compounds and/or fluoro compounds. In the case of a mixture ofdifferent pasty fatty substances, the hydrocarbon-based pasty compounds(containing mainly hydrogen and carbon atoms and optionally estergroups) may be used in major proportion.

Among the pasty compounds which may be used in the composition accordingto the invention, mention may be made of lanolins and lanolinderivatives such as acetylated lanolins or oxypropylenated lanolins orisopropyl lanolate, having a viscosity of from 18 to 21 Pa·s, forinstance 19 to 20.5 Pa·s, and/or a melting point of from 30° C. to 55°C. and for example from 30° C. to 40° C., and mixtures thereof. It isalso possible to use esters of fatty acids or of fatty alcohols, such asthose containing from 20 to 65 carbon atoms (melting point of about from20° C. to 35° C. and/or viscosity at 40° C. ranging from 0.1 to 40Pa·s), such as triisostearyl citrate or cetyl citrate; arachidylpropionate; polyvinyl laurate; cholesterol esters, such as triglyceridesof plant origin, such as hydrogenated plant oils (hydrogenated castoroil), viscous polyesters such as poly(12-hydroxystearic acid);polydimethylsiloxanes (PDMS) having alkyl or alkoxy pendant chainscontaining from 8 to 24 carbon atoms, and a melting point of 20-55° C.and form example form 20° C. to 40° C., such as stearyldimethicones (inparticular DC2503 and DC25514 from Dow Corning); and mixtures thereof.

The at least one pasty fatty substance may be present in a proportion upto 60% by weight, relative to the total weight of the composition, forexample from 0.5% to 45% by weight, and, as a further example, from 2%to 30% by weight, in the composition, if present.

In one aspect, the present invention provides a personal carecomposition comprising ETPEA and at least one film-forming siliconeresin. In one embodiment, the at least one film-forming silicone resinis chosen from silsesquioxanes and siloxysilicates. The use of siliconepolymers or derivatives as film-forming agents in cosmetic compositionsis known in the art. See, e.g., U.S. Pat. Nos. 5,965,112, 5,800,816,5,911,974, and 5,959,009. Silicone resin nomenclature is known in theart as “MDTQ” nomenclature, whereby a silicone resin is describedaccording to the various monomeric siloxane repeating units which makeup the polymer. Each letter of “MDTQ” denotes a different type of unit.The symbol M denotes the monofunctional unit (CH₃)₃SiO_(1/2). This unitis considered monofunctional because the silicone atom only shares oneoxygen for the formation of the chain. At least one of the methyl groupscan be replaced, such as, for example, to give a unit with formula[R(CH₃)₂]SiO_(1/2) where R is other than a methyl group. The symbol “D”denotes the difunctional unit (CH₃)₂SiO_(2/2), where two of theavailable bonds from the silicone atom are used for binding to oxygenfor the formation of the polymeric chain. The “D” unit is the majorbuilding block of dimethicone oils. The symbol “T” denotes thetrifunctional unit, (CH₃)SiO_(3/2), where three of the available bondsfrom the silicone atom are used for binding to oxygen for the formationof the polymeric chain. As in the “M” unit, any methyl group could bereplaced in “D” or “T” with a group R which is other than methyl.Finally, the symbol “Q” denotes a quadrifunctional unit SiO_(4/2), whereall four of the available bonds from the silicone atom are used forbinding to oxygen for the formation of the polymeric chain.

The number of different silicones which can be manufactured isstaggering. It would be clear to one skilled in the art that theproperties of each of the silicones will vary depending on the type ofmonomer, the type of substitution, the size of the polymeric chain, andthe degree of cross linking or size of the side chain. Differentproperties are attained depending on whether the backbone is a siliconechain with carbon-based side chains or whether the backbone iscarbon-based with silicone side chains.

As described above, the at least one film-forming silicone resin may, inone embodiment, be chosen from siloxysilicates and silsesquioxanes. Anysiloxysilicates or silsesquioxanes that functions as a film-former iswithin the practice of the invention. In one embodiment, the at leastone film-forming silicone resin is chosen from substitutedsiloxysilicates and silsesquioxanes. A substituted siloxysilicate or asubstituted silsesquioxane may be, for example, a siloxysilicate or asilsesquioxane where a methyl group has been substituted with a longercarbon chain such as an ethane, propane, or butane chain. The carbonchain may be saturated or unsaturated.

In one embodiment, the at least one film-forming silicone resin ischosen from siloxysilicates such as trimethylsiloxysilicates, which arerepresented by the following formula: [(CH₃)₃—Si—O]_(x)—(SiO_(4/2))_(y)(MQ units), where x and y can have values ranging from 50 to 80. In afurther embodiment, a siloxysilicate may be chosen from any combinationof M and Q units, such as, for example, [(R)₃—Si—O]_(x)—(SiO_(4/2))_(y),where R is chosen from methyl groups and longer carbon chains.

In a further embodiment, the film-forming silicone resin is chosen fromsilsesquioxanes that are represented by the following formula:(CH₃SiO_(3/2))_(x) (T units), where x has a value of up to severalthousand and the CH₃ may be replaced by an R, as described above for Tunits. In one embodiment, the silsesquioxane is chosen frompolymethylsilsesquioxanes, which are silsesquioxanes that do not have asubstituent replacing the methyl group. The polymethylsilsesquioxanesuseful in the present invention are film-formers and can, for example,have about 500 or less T units, such as, for example, from about 50 toabout 500 T units.

In one embodiment of the invention, the film forming silicone resinshave a melting point ranging from about 40° C. to about 80° C. Thesesilicone resins are soluble or dispersible in volatile silicones orother organic liquids. In one embodiment, the at least one film-formingsilicone resins may be solid at about 25° C. In one embodiment, the atleast one film-forming silicone resins may have a molecular weightranging from 1000 to 10,000 grams/mole. In one embodiment, the at leastone film-forming silicone resin is present in the composition in anamount ranging from 0.5% to 20% by weight, relative to the total weightof the composition, such as, for example, ranging from 1% to 10%.

Not all polymethylsilsesquioxanes are film-formers. For example, thehighly polymerized polymethylsilsesquioxanes (T Resins), such asTospearl™ from Toshiba or KMP590 from Shin-Etsu are highly insoluble,and therefore are not effective film-formers. The molecular weight ofthese polymethylsilsesquioxanes is difficult to determine, and theygenerally contain a thousand or more T units.

An example of a polymethylsilsesquioxane useful in accordance with thepresent invention is Belsil PMS MK, also referred to as Resin MK,available from Wacker Chemie. This polymethylsilsesquioxane is a polymerprimarily formed of polymerized repeating units of CH₃SiO_(3/2) (Tunits), and which can also contain up to about 1% (by weight or by mole)of (CH₃)₂SiO_(2/2) (D units). It is believed that the polymers are in a“cage” and “ladder” configuration, as exemplified in the figure below.The weight-average molecular weight of the “cage” unit has beencalculated to be 536. The majority of the polymer is in the “ladder”configuration, where the ends are capped with ethoxy (CH₃CH₂O) groups.The weight percent of ethoxy present is about 4.5%, and the mole percentis about 7% (silicone units). Since this functionality can react withwater, a small and variable amount of SiOH can also be present. Theweight-average molecular weight can be, for example, from about 500 toabout 50,000, such as about 10,000.

Polymethylsilsesquioxanes suitable for use in the present invention alsoinclude KR-220L available from SHIN-ETSU. The structure of KR-220L ismade up of mostly silicone T-units (CH₃SiO_(3/2)), with Si—OH or silanolend units. There are no D units. Other polymethylsilsesquioxanes thatcan be useful in the practice of the invention include KR-242A, whichhas a structure of about 98% methyl T units and about 2% dimethyl Dunits, with Si—OH or silanol end units, and KR-251, which has astructure of about 88% methyl T units and about 12% dimethyl D units,with Si—OH or silanol end units, both of which are available fromSHIN-ETSU.

In one embodiment of the invention, the at least one film-formingsilicone resin is chosen from combinations of M, D, T, and Q unitscomprising at least two units chosen from M, D, T, and Q, which satisfythe relationship R_(n)SiO_((4-n)/2) wherein n is a value ranging from1.0 to 1.50. Some resins of this type are disclosed in U.S. Pat. No.6,074,654. R may be a methyl group or any carbon chain as long as thesilicone resin retains its film-forming properties. Up to 5% of silanolor alkoxy functionality may also be present in the resin structure as aresult of processing.

In a further embodiment, the at least one film-forming silicone resincomprises repeating M units and Q units. The ratio of M units to Q unitsmay be, for example, about 0.7:1. The at least one film-forming siliconeresin may be chosen, for example, from Wacker 803 and 804, availablefrom Wacker Silicones Corporation and G.E. 1170-002 from GeneralElectric.

In a further embodiment, the at least one film-forming silicone resin isa copolymer, wherein at least one unit of the copolymer is chosen fromM, D, T, and Q silicone units, and wherein at least one additional unitof the copolymer is chosen from an ester. The at least one film-formingsilicone resin may be chosen from, for example, diisostearoyltrimethylolpropane siloxysilicates, such as SF 1318, available from GESilicones.

The compositions according to the present invention can additionallycomprise at least one additional film-former. The at least oneadditional film-former may improve, for example, smoothness orspreadability, water-resistance, transfer resistance properties, orother cosmetic or pharmaceutical properties desired by one of skill inthe art. The at least one additional film former may be chosen from, forexample, polyethylene, vinylpyrrolidone/vinyl acetate (PVP/VA)copolymers such as the Luviskol® VA grades (all ranges) from BASF®Corporation and the PVP/VA series from ISP, acrylic fluorinated emulsionfilm formers including Foraperle® film formers such as Foraperle® 303 Dfrom Elf Atochem (although Foraperle® may not be appropriate for somecosmetic formulations) GANEX® copolymers such as butylated PVP,PVP/Hexadecene copolymer, PVP/Eicosene copolymer or tricontanyl,Poly(vinylpyrrolidone/diethylaminoethyl methacrylate) orPVP/Dimethylaminoethylmethacrylate copolymers such as Copolymer 845,Resin ACO-5014 (Imidized IB/MA copolymer), other PVP based polymers andcopolymers, alkyl cycloalkylacrylate copolymers (See, e.g., WO98/42298), Mexomere® film formers and other allyl stearate/vinyl acetatecopolymers (allyl stearate/VA copolymers), polyolprepolymers such asPPG-12/SMDI copolymer, polyolprepolymers such as PPG-12/SM DI copolymer,Poly(oxy-1,2-ethanediyl), α-hydro-(ω-hydroxy-polymer with1,1′-methylene-bis-(4-isocyanatocyclohexan available from Barnet,Avalure™ AC Polymers (Acrylates Copolymer) and Avalure™ M UR polymers(Polyurethane Dispersions), available from B.F. Goodrich.

The at least one additional film former which also may be used withinthe framework of the invention includes film formers having any filmformer chemistry known in the art such as, for example, PVP, acrylates,urethane, synthetic polymers of the polycondensate type, free-radicaltype, or ionic type, polymers of natural origin, and mixtures thereof,as well as any other film former known within the practice of thecosmetic and pharmaceutical arts which one skilled in the art maydetermine to be compatible.

An appropriate amount of the at least one additional film-former may bedetermined by one of skill in the art, and can vary considerably basedon the application. For example, in one embodiment, the at least oneadditional film-former may be used in an amount ranging from 0.1% to20%, such as, for example, ranging from 1% to 10%, by weight, relativeto the total weight of the composition.

The amounts of the at least one film-forming silicone resin and of theat least one structuring polymer, e.g., a polyamide polymer, may bechosen according to the desired hardness and desired stability of thecompositions, and according to the specific application envisaged. Therespective amounts of the at least one structuring polymer, e.g., apolyamide polymer, and of the at least one film-forming silicone resincan be such that a disintegrable solid which does not flow under its ownweight is obtained.

In one aspect, the present invention provides a composition comprising,in a physiologically acceptable medium, fibers and ETPEA, thecomposition being intended in particular for cosmetics. The inventionalso relates to a cosmetic make-up or care process for keratin materialsusing the fiber-containing composition. The make-up or care process andcomposition according to the invention are intended more particularlyfor the keratin materials of human beings, such as the skin (includingthe scalp), the nails, keratin fibers, especially substantially longlinear keratin fibers, such as the eyelashes, the eyebrows and the hair.In one aspect, the present invention provides a mascara with ETPEA andfibers.

The composition according to the invention can be in the form of acoating composition for the eyelashes (in particular a mascara), aneyeliner, a product for the eyebrows, a product for the lips, a facepowder, an eyeshadow, a foundation, a make-up product for the body, aconcealer product, a nail varnish, a skincare product, including aproduct for scalp care, or a hair care product (hair mascara or spray).

It is known practice to use fibers in make-up products, especially fortheir lengthening effects in mascaras (see JP-A-57/158 714 andJP-A-3-153 613), their moisturizing properties in lipsticks (seedocument U.S. Pat. No. 5,498,407), to improve the contours of lipstickon the edges of the lips (see document EP-A-0 106 762) or to improve thecondition of broken nails (see FR-A-1 529 329) or in skincare productsfor their velvety feel (see JP-A-7/196 440). The present inventionutilizes these fibers in combination with ETPEA to form a cosmetic. Inone aspect, the ETPEA is present in the composition according to theinvention in a content ranging from 0.01% to 10% by weight, relative tothe total weight of the composition, preferably ranging from 0.05% to 5%by weight and better still ranging from 0.1% to 3% by weight.

According to the invention, the composition contains one or more fibers.The term “fiber” means any particle that is solid at room temperatureand atmospheric pressure, whose length is greater than its apparentdiameter, used alone or in combination, and which is insoluble in theingredients of the composition, even when these ingredients are raisedto a temperature above room temperature and in particular to theirsoftening point or their melting point. These fibers are advantageouslychemically inert, i.e., they do not react chemically with the variousingredients of the composition. These fibers have melting points thatare at least greater than 170° C. and better still greater than 200° C.They may be absorbent or non-absorbent, i.e., capable in particular ofabsorbing the oils of the composition and also the biological substancessecreted by the skin.

The fibers that can be used in the composition of the invention may befibers of synthetic or natural, and inorganic or organic origin. Theymay be short or long, flat, cylindrical or lamellar, individual ororganized, for example in bundles, and hollow or solid. They can haveany shape, and in particular a circular, elliptic or polygonal(triangular, square, hexagonal or octagonal) cross section depending onthe specific application envisaged. In particular they can have bluntand/or rounded ends to prevent injury. Their ends may also bemultilobal, in particular trilobal, pointed or rounded. In particular,the fibers have a length ranging from 1 nm to 20 mm, preferably from 10nm to 5 mm and better still from 0.1 mm to 1.6 mm. Their cross sectioncan be within a circle of diameter D ranging from 2 nm to 150 μm,preferably ranging from 20 nm to 120 μm and better still from 500 nm to80 μm. The weight or yarn count of the fibers is often given in denieror decitex and represents the weight in grams per 9 km of yarn. Thefibers in the composition according to the invention preferably have ayarn count chosen in the range from 0.15 to 30 denier and better stillfrom 0.18 to 18 denier. Advantageously, the fibers have a length L and adiameter D such that L/D is chosen in the range from 1.5 to 2500,preferably from 3.5 to 500 and better still from 5 to 150.

The fibers can be those used in the manufacture of textiles, and inparticular silk, cotton, wool or flax fibers, cellulose fibers extractedin particular from wood, plants or algae, polyamide (Nylon®), cork,sugar cane, rayon or viscose fibers, acetate fibers, in particular rayonacetate or cellulose acetate fibers, poly-(p-phenylene terephthalimide)(or aramide) fibers, in particular Kevlar® fibers, acrylic polymerfibers, in particular polymethyl methacrylate (PMMA) orpoly-2-hydroxyethyl methacrylate fibers, polyolefin fibers and inparticular polyethylene or polypropylene fibers, glass, silica or carbonfibers, in particular in graphite form, polytetrafluoroethylene(Teflon®), insoluble collagen, polyester, polyvinyl chloride orpolyvinylidene chloride, polyvinyl alcohol, polyacrylonitrile, chitosan,polyurethane or polyethylene phthalate fibers, fibers formed from amixture of polymers such as those mentioned above, for instancepolyamide/polyester fibers, and mixtures thereof.

It is also possible to use surgical fibers, such as resorbable syntheticfibers prepared from glycolic acid and from ε-caprolactone (“Monocryl”from Johnson & Johnson), resorbable synthetic fibers such as thecopolymer of lactic acid and of glycolic acid (“Vicryl” from Johnson &Johnson), terephthalic polyester fibers (“Ethibond” from Johnson &Johnson) and stainless steel threads (“Steel” from Johnson & Johnson) inparticular for use as nail varnishes.

Moreover, the fibers may or may not be surface-treated and may or maynot be coated, in particular with a view to making them hydrophobic. Ascoated fibers which can be used in the invention, mention may be made ofpolyamide fibers coated with copper sulfide for an antistatic effect(for example the R-STAT fibers from Rhodia) or another polymer allowinga particular organization of the fibers (specific surface treatment) ora surface treatment which induces color/hologram effects (“Lurex” fiberfrom Sildorex, for example).

Flat multilayer fibers having goniochromatic properties may also beused. Such fibers are disclosed in particular in the document.Multilayer polymer fibers are disclosed in particular in document EP-A-0921 217. They are formed from alternating layers of polyamide

The fibers which can be used in the composition according to theinvention are preferably polyamide or poly-(p-phenylene terephthalimide)fibers for a first polymer with a polyamide unit. Their length (L) canrange from 0.1 to 5 mm, preferably from 0.25 to 1.6 mm, and theiraverage diameter (D) can range from 5 to 50 μm. In particular, thepolyamide fibers sold by Etablissements P. Bonte under the namePolyamide 0.9 Dtex 3 mm, having an average diameter ranging from 15 μmto 20 μm, a weight of about (0.9 dtex) and a length ranging from 0.3 mmto 1.5 mm, can be used. Poly-(p-phenylene terephthalamide) fibers withan average diameter of 12 μm and a length of about 1.5 mm can also beused, such as those sold under the name Kevlar Floc by the company DuFont Fibers.

The fibers may be present in the composition according to the inventionin a content ranging from 0.1% to 40% by weight, relative to the totalweight of the composition, in particular ranging from 0.5% to 30% byweight, preferably ranging from 1% to 20% by weight and better stillfrom 1% to 10% by weight. Advantageously, the first polymer and thefibers may be present in the composition according to the invention in afibers/first polymer weight ratio which may range from 0.5 to 4,preferably ranging from 0.9 to 2.5.

In one aspect, the cosmetic composition of the present inventionincludes ETPEA and a gelling agent, i.e., an agent with gelling abilitythat is not ETPEA. This at least one gelling agent is chosen fromliposoluble and lipodispersible rheological agents, such as agents thatare soluble or dispersible in the fatty phase that is liquid at roomtemperature and atmospheric pressure. The at least one gelling agent maybe chosen from gelling agents in polymeric form and gelling agents inmineral form. In one embodiment, the at least one gelling agent may bein mineral form with particle sizes that cause little or no lightscattering. Thus, it may be possible to obtain a translucent or eventransparent composition. In one embodiment, the at least one gellingagent is not soluble in an aqueous phase or in water.

Fatty-phase gelling agents or rheological agents which can be used inthe invention may be chosen from lipodispersible mineral particles suchas optionally modified clays and optionally modified silica, for examplewhich have been hydrophobic-treated, as well as polymeric gelling agentssuch as partially or totally crosslinked elastomeric polyorganosiloxanesof three-dimensional structure; galactomannans comprising from 1 to 6hydroxyl groups, for example 2 to 4 hydroxyl groups, per saccharide,substituted with a saturated or unsaturated alkyl chain; polymers orcopolymers resulting from the polymerization or copolymerization of anethylenic monomer, comprising one or more ethylenic, preferablyconjugated bonds (or dienes); silicone gums; ethylcellulose, such as theproducts sold under the name Ethocel by Dow Chemical; and mixturesthereof.

As modified clays which can be used, mention may be made of hectoritesmodified with an ammonium chloride of a C₁₀ to C₂₂ fatty acid, such ashectorite modified with distearyldimethylammonium chloride, also knownas quatermium-18 bentonite, such as the products sold or made under thenames Bentone 34 by the company Rheox, Claytone XL, Claytone 34 andClaytone 40 sold or made by the company Southern Clay, the modifiedclays known under the name quaternium-18 benzalkonium bentonites andsold or made under the names Claytone HT, Claytone GR and Claytone PS bythe company Southern Clay, the clays modified withstearyldimethylbenzoylammonium chloride, known as stearylalkyloniumbentonites, such as the products sold or made under the names ClaytoneAPA and Claytone AF by the company Southern Clay, and Baragel 24 sold ormade by the company Rheox.

As polyorganosiloxanes which can be used in the invention, mention maybe made of the crosslinked elastomeric polyorganosiloxanes described inapplication EP-A-0,295,886, the disclosure of which is incorporatedherein by reference. According to that application, they are obtained byaddition reaction and crosslinking, in the presence of a platinum-typecatalyst, of at least:

-   -   (a) a polyorganosiloxane having at least two C₂ to C₆ lower        alkenyl groups per molecule; and    -   (b) a polyorganosiloxane having at least two hydrogen atoms        linked to a silicon atom per molecule. It is also possible to        use the polyorganosiloxanes described in U.S. Pat. No.        5,266,321, the disclosure of which is incorporated by reference        herein. According to that patent, they are chosen in particular        from:    -   i) polyorganosiloxanes comprising R₂SiO and RSiO_(1.5) units and        optionally R₃SiO_(0.5) and/or SiO₂ units in which the radicals        R, independently of each other, are chosen from a hydrogen, an        alkyl such as methyl, ethyl or propyl, an aryl such as phenyl or        tolyl, an unsaturated aliphatic group such as vinyl, the weight        ratio of the units R₂SiO to the units RsiO_(1.5) ranging from        1/1 to 30/1;    -   ii) polyorganosiloxanes which are insoluble and swellable in        silicone oil, obtained by addition of an        polyorganohydrogenosiloxane (1) and of a polyorganosiloxane (2)        having unsaturated aliphatic groups such that the amount of        hydrogen or of unsaturated aliphatic groups in (1) and (2)        respectively ranges from 1 to 20 mol % when the        polyorganosiloxane is non-cyclic and from 1 to 50 mol % when the        polyorganosiloxane is cyclic. Optionally, these        polyorganosiloxanes can comprise from 1 to 40 oxyalkylene        groups, such as oxypropylene and/or oxyethylene groups.

As examples of polyorganosiloxanes which can be used according to theinvention, mention may be made of those sold or made under the namesKSG6 from Shin-Etsu, Trefil E-505C or Trefil E-506C from Dow-Corning,Gransil from Grant Industries (SR-CYC, SR DMF10, SR-DC556) or thosemarketed in the form of preconstituted gels (KSG15, KSG17, KSG16, KSG18,KSG21 from Shin-Etsu, Gransil SR 5CYC gel, Gransil SR DMF 10 gel,Gransil SR DC556 gel, SF 1204 and JK 113 from General Electric. Amixture of these commercial products may also be used.

As alkyl galactomannans which can be used in the invention, mention maybe made of guar gum or carob gum alkylated with C₁ to C⁻⁶, for example,C₁ to C₃ alkyl chains, such as ethyl or propyl guar having a degree ofsubstitution of 2 to 3, for example, of about 2.5 to 2.8, as describedin document EP-A-708 114 and sold or made by the company Aqualon underthe name N-Hance-AG 200® or N-Hance AG 50®.

As polymers or copolymers resulting from the polymerization orcopolymerization of an ethylenic monomer, use may be made of vinyl,acrylic or methacrylic copolymers which may be block copolymers, such asdiblock or triblock copolymers, or even multiblock or starburst orradial copolymers. The at least one ethylenic gelling agent maycomprise, for example, a styrene block (S), an alkylstyrene block (AS),an ethylene/butylene block (EB), an ethylene/propylene block (EP), abutadiene block (B), an isoprene block (I), an acrylate block (A), amethacrylate block (MA) or a combination of these blocks.

In one embodiment, a copolymer comprising at least one styrene block isused as gelling agent or ethylenic rheological agent. A triblockcopolymer and in particular those of the polystyrene/polyisoprene orpolystyrene/polybutadiene type, such as those sold or made under thename “Luvitol HSB” by BASF and those of thepolystyrene/copoly(ethylene-propylene) type or alternatively of thepolystyrene/copoly(ethylene/butylene) type, such as those sold or madeunder the brand name “Kraton” by Shell Chemical Co. or Gelled Permethyl99A by Penreco, may be used. Styrene-methacrylate copolymers can also beused.

As an ethylenical rheological agent which can be used in the compositionof the invention, mention may be made, for example, of Kraton (G1650(SEBS), Kraton G1651 (SEBS), Kraton G1652 (SEBS), Kraton G1657X (SEBS),Kraton G1701X (SEP), Kraton G1702X (SEP), Kraton G1726X (SEB), KratonG1750X (EP) multiarm, Kraton G1765X (EP) multiarm, Kraton D-1101 (SBS),Kraton D-1102 (SBS), Kraton D-1107 (SIS), Gelled Permethyl 99A-750,Gelled Permethyl 99A-753-58 (mixture of starburst block polymer andtriblock polymer), Gelled Permethyl 99A-753-59 (mixture of starburstblock polymer and triblock polymer), Versagel 5970 and Versagel 5960from Penreco (mixture of starburst polymer and triblock polymer inisododecane), and OS 129880, OS 129881 and OS 84383 from Lubrizol(styrene-methacrylate copolymer).

As other rheological agents which can be used in the invention, mentionmay be made of silicone gums. The silicone gum has organic groups (R₇,R₈, R₉, R₁₀, R₁₁ and R₁₂) attached to the silicon atoms, the siliconatoms being separated by oxygen atoms (i.e.,X—Si(R₇)(R₈)—O—Si(R₉)(R₁₀)—O—Si(R₁₁)(R₁₂)—X. In general, R₇, R₈, R₁₁,and R₁₂ are identical or different, and each is chosen from alkylradicals comprising from 1 to 6 carbon atoms; R₉ and R₁₀ are identicalor different, and each is chosen from alkyl radicals comprising from 1to 6 carbon atoms and aryl radicals and X is chosen from alkyl radicalscomprising from 1 to 6 carbon atoms, a hydroxyl radical and a vinylradical. The number of Si(R)(R) units are chosen so as to give thesilicone gum a viscosity of greater than 100 000 mPa·s, such as greaterthan 500 000 mPa·s. In general, the silicon gum has about 3,000 to 8,000silicon atoms. Suitable silicon gums include the product sold or madeunder the name SE30 by the company General Electric; the product sold ormade under the name AK 500 000 by the company Wacker; the product soldor made under the name Q2-1401 by the company Dow Corning; the productsold or made under the name Q2-1403 by the company Dow Corning, and theproduct sold or made under the name 761 by the company Rhone-Poulenc(Rhodia Chimie).

As other gelling agents or rheological agents which can be used in theinvention, mention may be made of silica, such as fumed silica. Thefumed silica may have a particle size which may be nanometric tomicrometric, for example ranging from about 5 nm to 200 nm.

The fumed silicas may be obtained by high-temperature hydrolysis of avolatile silicon compound in a hydrogen-oxygen flame, producing a finelydivided silica. This process makes it possible to obtain hydrophilicsilicas which have a large number of silanol groups at their surface.Such hydrophilic silicas are sold or made, for example, under the names“Aerosil 130®”, “Aerosil 200®”, “Aerosil 255®”, “Aerosil 300®” and“Aerosil 380®” by the company Degussa, and “CAB-O-SIL HS-5®”, “CAB-O-SILEH-5®”, “CAB-O-SIL LM-130®”, “CAB-O-SIL MS-55®” and “CAB-O-SIL M-5®” bythe company Cabot.

It is thus possible to chemically modify the surface of the hydrophilicsilica by chemical reaction, producing a reduction in the number ofsilanol groups. The silanol groups can be replaced, for example, withhydrophobic groups: this then gives a hydrophobic silica. Thehydrophobic groups may be:

-   -   trimethylsiloxyl groups, which are obtained in particular by        treating fumed silica in the presence of hexamethyldisilazane.        Silicas thus treated are known as “silica silylate” according to        the CTFA (6th edition, 1995). They are sold or made, for        example, under the references “Aerosil R812®” by the company        Degussa and “CAB-O-SIL TS-530®” by the company Cabot;    -   dimethylsilyloxyl or polydimethylsiloxane groups, which are        obtained in particular by treating fumed silica in the presence        of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus        treated are known as “silica dimethyl silylate” according to the        CTFA (6th edition, 1995). They are sold or made, for example,        under the references “Aerosil R972®” and “Aerosil R974®” by the        company Degussa, and “CAB-O-SIL TS-610®” and “CAB-O-SIL TS-720®”        by the company Cabot;    -   groups derived from reacting fumed silica with silane alkoxides        or siloxanes. These treated silicas are, for example, the        products sold or made under the reference “Aerosil R805®” by the        company Degussa.

According to the invention, a hydrophobic silica, such as a fumedsilica, may be used as lipophilic gelling agent or rheological agent.The use of fumed silica makes it possible to obtain a translucent oreven transparent composition, in particular in the form of a stick whichdoes not exude, in the absence of opacifying particles such as waxes,fillers and pigments (including nacres).

The at least one liposoluble rheological agent can allow the exudationof the composition to be limited and can allow its stability to beincreased, while at the same time conserving the composition's glossyappearance, which is not possible with waxes such as those usedconventionally in cosmetics and dermatology. These gelling agents can beused, for example, at concentrations of from 0.05% to 35% relative tothe total weight of the composition, for example from 0.5% to 20% orfrom 1% to 10%.

The gels of the invention may be formulated into personal care productsaccording to techniques well known in the art. The gel may be combinedwith ingredients conventionally incorporated into personal care productssuch as chelating agents, colorants, emulsifiers, fillers, hardeners,perfumes, strengtheners, water and wax, to name a few. Such additivesare well known in the art, and are also set forth in, e.g., thefollowing documents, all incorporated by reference herein in theirentirety: U.S. Pat. No. 3,255,082 to Barton, U.S. Pat. No. 4,049,792 toElsnau, U.S. Pat. No. 4,137,306 to Rubino et al., and U.S. Pat. No.4,279,658 to Hooper et al. See also U.S. Pat. Nos. 3,148,125 and5,538,718 (describing the formulation of lipstick and other cosmeticsticks). See also European Patent Application Nos. 1 068 855 A1 and 1068 856 A1, where the disclosure of these two documents is incorporatedherein by reference, where these documents provide additionalformulation suggestions for incorporating an organic gellant into acosmetic or other personal care product, where these formulationsuggestions may be employed to formulate a corresponding product withthe ETPEA gellant of the present invention in place of some or all ofthe gallants, e.g., the UNICLEAR™ 80 and 100 gellants, disclosedtherein.

Personal care products may be prepared from the ETPEA resin of theinvention by mixing the various components of the product at an elevatedtemperature and then cooling in order to form the gelled (solidified)composition. Desirably, any volatile components are added to the mixtureat a relatively late stage of the mixing, so as to limit volatilizationof the component. Preferably, the liquid and ETPEA gelling agent aremixed and heated so as to fully dissolve the ETPEA in the liquid (e.g.,at 80° C.-150° C.). An active ingredient (e.g., active antiperspirant)can be added after the ETPEA fully dissolves, and mixing then takesplace. Mixing may continue during cooling, with colorant or othercomponent being added during the cooling stage.

Thus, the present invention provides a personal care product comprisinga resin composition prepared by reacting components comprising dibasicacid, diamine, polyol and monoalcohol, wherein at least 50 equivalentpercent of the dibasic acid comprises polymerized fatty acid; and atleast 50 equivalent percent of the diamine is ethylene diamine. Thepersonal care product preferably further comprises at least onecosmetically active ingredient and/or at least one dermatologicallyactive ingredient. The personal care product may constitute acomposition for the care and/or treatment and/or making-up of keratinoussubstances. Suitable compositions include makeup products for the lipssuch as lipstick and lip pencils, and also for the care and/or treatmentof the skin, including the scalp and lips, such as care creams applieddaily, sunscreen for the lips and skin, makeup products for the skin,body hygiene products such as deodorants in particular as sticks, and toeye makeup products such as eye liners, in particular in the form of apencil or mascaras, notably in the form of a cake.

In addition, the present invention provides a controlled releasecomposition comprising a volatile component and a resin compositionprepared by reacting components comprising dibasic acid, diamine, polyoland monoalcohol, wherein at least 50 equivalent percent of the dibasicacid is or comprises polymerized fatty acid; and at least 50 equivalentpercent of the diamine is ethylene diamine.

Further, the ETPEA resins of the present invention may be combined witha suitable solvent so as to form a gel, where the gel in combinationwith a wick forms a candle. Thus, in one aspect, the present inventionprovides a candle comprising a wick and a resin composition prepared byreacting components comprising dibasic acid, diamine, polyol andmonoalcohol, wherein (a) at least 50 equivalent percent of the dibasicacid comprises polymerized fatty acid; (b) at least 50 equivalentpercent of the diamine comprises ethylene diamine; (c) 10-60 equivalentpercent of the total of the hydroxyl and amine equivalents provided bydiamine, polyol and monoalcohol are provided by monoalcohol; and (d) nomore than 50 equivalent percent of the total of the hydroxyl and amineequivalents provided by diamine, polyol and monoalcohol are provided bypolyol; the candle further comprising a solvent that is gelled by theresin. In one aspect, the candle contains icons. An exemplary icon is asecond gelled phase, preferably visually distinct from the gel formedfrom ETPEA. The icon(s) may be embedded within the candle, or may be onthe surface of the candle. The second gelled phase may be, but need notbe, ETPEA. In one aspect, the second gelled phase is transparent.

The candle may, in one aspect, contain hydrocarbon, where thehydrocarbon and the ETPEA resin form a gel. The candle may also, in oneaspect, contain a fragrance material. Furthermore, the candle maycontain an ester.

Methods of using gels to form candles, including wicks, icons, the useof hydrocarbons, suitable fragrance materials, and suitable esters, arewell known in the candle-making art, where these methods and componentsmay be used to prepare candles from EPTEA resins.

Again, in regard to the preparation of, and components used in, candles,personal care products, and fragrance-releasing compositions, referenceis made U.S. Pat. Nos. 3,615,289, 3,645,705, 6,111,055, 6,129,771 and6,214,063 (describing the formulation of candles and pigmented objectsembedded in candle, which are an example of an “icon”); U.S. Pat. Nos.3,148,125 and 5,538,718 (describing the formulation of lipstick andother cosmetic sticks); and U.S. Pat. Nos. 4,275,054, 4,937,069,5,069,897, 5,102,656 and 5,500,209 (describing the formulation ofdeodorant and/or antiperspirant).

The following examples are set forth as a means of illustrating thepresent invention and are not to be construed as a limitation thereon.

Methodology

The hardness of a composition may be measured according to a method ofpenetrating a probe into said composition and in particular using atexture analyzer (for example TA-XT2 from Rheo) equipped with an ebonitecylinder of height 25 mm and diameter 8 mm. The hardness measurement iscarried out at 20° C. at the center of 5 samples of said composition.The cylinder is introduced into each sample of composition at apre-speed of 2 mm/s and then at a speed of 0.5 mm/s and finally at apost-speed of 2 mm/s, the total displacement being 1 mm. The recordedhardness value is that of the maximum peak observed. The measurementerror is about ±50 g.

Hardness may also be measured by a “cheese wire” method, which involvescutting an 8.1 mm tube of composition and measuring its hardness at 20°C. using a DFGHS 2 tensile testing machine from Indelco-Chatillon Co. ata speed of 100 mm/minute. The hardness value from this method isexpressed in grams as the shear force required to cut a stick under theabove conditions. According to this method, the hardness of compositionsaccording to the present invention which may be in stick form may rangefrom 30 g to 150 g, such as from 30 g to 120 g, and further such as from30 g to 50 g.

The hardness of the composition of the present invention may be suchthat the compositions are self-supporting and can easily disintegrate toform a satisfactory deposit on a keratinous material. In addition, thishardness may impart good impact strength to the inventive compositionswhich may be cast in stick form.

Turbidity may be measured using a model 2100 P turbidimeter from Hach atambient temperature (20 to 25° C.). The tubes used for the measurementare referenced AR 397 A cat 24347-06. The device is calibrated usingformazine suspensions with different concentrations. The turbidity ismeasured in terms of Nephelometric Turbidity Units (NTU).

EXAMPLES Example A

The following reactants and relative reactant amounts were used toprepare an ETPEA resin:

Reactant Equivalents Weight Percent PRIPOL ™ 1015 dimer acid 100 76.7Stearyl alcohol 28 17.3 Neopentyl glycol 16 2.0 Ethylenediamine 56 4.0

The ETPEA was synthesized by charging the PRIPOL™ 1015 dimer acid,steraryl alcohol and neopentyl glycol to a reaction vessel at roomtemperature, heating the mixture to 100° C., adding the ethylenediamine,heating to 220° C. and holding for 3 hours, and holding under vacuum(8-10 mbar) at 220° C. for 2 hours. The ETPEA had a softening point of76.7° C. and a color of 596 (APHA).

Example B

The following reactants and relative reactant amounts were used toprepare an ETPEA resin:

Reactant Equivalents Weight Percent EMPOL ™ 1008 dimer acid 100 75.8Stearyl alcohol 25 17.1 Neopentyl glycol 25 3.3 Ethylenediamine 50 3.8

The ETPEA was synthesized following the procedure described in ExampleA, using the relative reactant amounts set forth in the above Table. Theproduct ETPEA has a softening point of 74.7° C. and a color of 238(APHA).

The following Examples 1-74, which are prophetic, illustrate theincorporation of ETPEA of either of Examples A or B into a personal careproduct. The following suppliers, provide components that may beincluded in compositions of the present invention: SCHERCEMOL™ DISMdilsostearyl malate may be obtained from Shear Chemical Inc. CERAPHYL™45 dioctyl malate may be obtained from ISP. CRISTAL™ O castor oil andNature Chem PGR propylene glycol ricinoleate may be obtained fromChaschem. PARSOL™ 1789 butyl methoxydibenzoyl methane may be obtainedfrom Givaudan-Roure. Neo Heliopan 303 octylcrylene may be obtained fromHaarman & Reimer. ETHOCEL™ ethyl cellulose may be obtained from DowChemical. The specific Examples 1-74 also identify various suppliersfrom which components for personal care products may be obtained.

Example 1 Lip Composition Formulation

ETPEA is solubilized with the aid of a polyglyceryl-2polyhydroxystearate in parleam oil, at 100° C., followed by addition ofpigments. The whole is mixed using a deflocculating turbomixer (Rayneri)and then cast in lipstick molds. A homogeneous stick of lipstick isobtained, where the hardness thereof may be measured using a TA-XT2texture analyzer at 20° C. In one aspect the lipstick is glossy andnon-migrating, as may be confirmed by a test with a panel of experts. Inone aspect, the lipstick of the present invention is glossier whenapplied than a lipstick of the prior art, and migrates less after beingworn for 2 hours. Percents (by weight) of the components of thecomposition reaction mixture are indicated in Table 1.

TABLE 1 Component Weight percent ETPEA 25.0 Parleam oil 56.0Polyglyceryl-2 polyhydroxystearate 10.0 Pigments (brown iron oxide +titanium oxide) 9.0

Example 2 Anhydrous Eyeshadow

An eyeshadow in stick form is prepared as in Example 1. In one aspectthe eyeshadow is glossy and non-migrating. Percents (by weight) of thecomponents of the composition reaction mixture are indicated in Table 2.

TABLE 2 Component Weight percent ETPEA 25.0 Parleam oil 35.1 Glyceryloleate 31.25 Pigments 8.65

Example 3 Mascara

In one aspect, the present invention provides a composition in the formof a mascara. Percents (by weight) of the components of the compositionreaction mixture are indicated in Table 3.

TABLE 3 Component Weight percent ETPEA 1.0 Carnauba wax 2.6 Beeswax 3.3Paraffin wax 10.4 Hydrogenated jojoba oil 0.2 Hydrogenated palm oil 0.22-Amino-2-methyl-1,3-propanediol 0.8 Triethanolamine 2.4 Stearic acid6.6 Hydroxyethylcellulose 0.8 Gum arabic 0.6 Ethyl acrylate/methylmethacrylate copolymer 7.0 AM (80/20) as an aqueous dispersioncontaining 50% AM (Daitosol 5000 AD from Saito) Black iron oxide 5.0Preserving agents q.s. Water q.s. 100.0

Example 4 Mascara

In one aspect, the present invention provides a composition in the formof a mascara. Percents (by weight) of the components of the compositionreaction mixture are indicated in Table 4.

TABLE 4 Component Weight percent ETPEA 1.0 Carnauba wax 4.6 Rice branwax 2.1 Paraffin 2.2 Beeswax 8.2 Talc 1.0 Bentonite 5.0 Vinylacetate/allyl stearate copolymer (65/35) 6.5 (Mexomer PQ from Chimex)Polyvinyl laurate (Mexomere PP from Chimex) 0.7 Sulphopolyester (AQ 55Sfrom Eastman 0.12 Chemical) Isododecane 53.9 Propylene carbonate 1.6Pigments 4.9 Preserving agents q.s. Water q.s. 100.0

Example 5 Mascara

a) In one aspect of the present invention, a dispersion ofnon-crosslinked copolymer of methyl acrylate and of acrylic acid in a95/5 ratio, in isododecane, is prepared according to the method ofExample 7 of document EP-A-749 747. A dispersion is thus obtained ofparticles of poly(methyl acrylate/acrylic acid) surface-stabilized inisododecane with a polystyrene/copoly-(ethylene-propylene) diblock blockcopolymer sold under the name Kraton G1701 (Shell), with a solidscontent of 24.2% by weight, a mean particle size of 180 nm and a Tg of20° C. This copolymer can form a film at room temperature.

b) In another aspect, the present invention provides for a compositionin the form of a mascara. Percents (by weight) of the components of thecomposition reaction mixture are indicated in Table 5.

TABLE 5 Component Weight percent ETPEA 0.5 Carnauba wax 4.7 Rice branwax 2.1 Paraffin 2.2 Beeswax 8.2 Talc 1.0 Bentonite 5.0 Vinylacetate/allyl stearate copolymer (65/35) 6.5 (Mexomer PQ from Chimex)Polyvinyl laurate (Mexomere PP from Chimex) 0.7 Dispersion of polymer inisododecane 10.0 according to a) Propylene carbonate 1.6 Pigments 4.9Preserving agents q.s. Isododecane q.s. 100.0

Example 6 Lip Balm

In one aspect, the present invention provides a composition in the formof a colored transparent lip balm, prepared, for example, in thefollowing manner. A dispersion of pigments is prepared in the presenceof dispersing agent. This dispersion is combined with a mixture of ETPEAand octyidodecanol heated to ca. 100° C., while maintaining the mixtureunder slow stirring over ca. 30 minutes. After casting in molds andcooling to ambient temperatures, a solid composition is obtained. Theturbidity of the composition may be measured as described herein, toprovide a turbidity value in units of NTU. Percents (by weight) of thecomponents of the composition reaction mixture are indicated in Table 6.

TABLE 6 Component Weight percent ETPEA 25.0 Octyldodecanol 10.0 Ironoxides 0.0006 SOLSPERSE ® 21000* 0.00002 Fragrance 4.0 Parleam oil q.s.100.0 *Dispersing agent sold by Avecia Pigments and Additifs.

Example 7 Scenting Gel

In one aspect, the present invention provides a composition in the formof a colored transparent anhydrous scenting gel for the body, preparedby mixing the ingredients as indicated in Table 7. The turbidity of thegel may be measured as described herein, in terms of NTU.

TABLE 7 Component Weight percent ETPEA 43.0 Pentacyclodimethicone 43.0Aluminum lake of brilliant blue FCF on 0.001 alumina (12/88) (Blue 1lake) SOLSPERSE ® 21000* 0.000025 Fragrance 4.0 Parleam oil q.s. 100.0*Dispersing agent sold by Avecia Pigments and Additifs.

Example 8 Mascara

In one aspect, the present invention provides a composition in the formof a mascara, prepared by mixing the ingredients as indicated in Table8. In a preferred aspect, the mascara obtained is easy to apply andadheres well to the eyelashes during and after application, giving theeyelashes a lengthened effect upon application.

TABLE 8 Component Weight percent ETPEA 1.0 Carnauba wax 2.6 Beeswax 3.3Paraffin wax 10.4 Hydrogenated jojoba oil 0.2 Hydrogenated palm oil 0.22-Amino-2-methyl-1,3-propanediol 0.8 Triethanolamine 2.4 Stearic acid6.6 Hydroxyethylcellulose 0.8 Gum arabic 0.6 Ethyl acrylate/methylmethacrylate copolymer 5.0 AM (80/20) as an aqueous dispersioncontaining 50% AM (Daitosol 5000 AD from Saito) Polyamide fibers (3 mmlong, 0.9 Dtex, from 1.0 the company Paul Bonte) Black iron oxide 5.0Preserving agents q.s. Water q.s. 100.0

Example 9 Mascara

In one aspect, the present invention provides a composition in the formof a mascara, prepared by mixing the ingredients as indicated in Table9. In a preferred aspect, the mascara obtained adheres well to theeyelashes during application, and allows the eyelashes to be made upquickly.

TABLE 9 Component Weight percent ETPEA 1.0 Carnauba wax 2.6 Beeswax 3.3Paraffin wax 10.4 Hydrogenated jojoba oil 0.2 Hydrogenated palm oil 0.22-Amino-2-methyl-1,3-propanediol 0.8 Triethanolamine 2.4 Stearic acid6.6 Hydroxyethylcellulose 0.8 Gum arabic 0.6 Ethyl acrylate/methylmethacrylate copolymer 5.0 AM (80/20) as an aqueous dispersioncontaining 50% AM (Daitosol 5000 AD from Saito) Polyamide fibers (3 mmlong, 0.9 Dtex, from 1.0 the company Paul Bonte) Black iron oxide 5.0Preserving agents q.s. Water q.s. 100.0

Example 10 Lipstick

In one aspect, the present invention provides a composition in the formof a lipstick, prepared, for example, in the following manner. Polyamidefibers are predispersed in an ETPEA/isoparaffin (Parleam) mixture usinga spatula. In one aspect, the resulting paste is ground in a three-rollmill. A separate reaction vessel is charged with ETPEA,2-octyldodecanol, Parleam, and pigments, and the charged components aremixed together with stirring, such as with a Raynerie turbomixer, atabout 1000 rpm and about 100° C. The reaction vessel is then furthercharged with the fiber predispersion, and the resulting reaction mixtureis stirred at about 800 rpm for about 30 minutes. The resultingpreparation is then cast in a lipstick mold, and placed at about −20° C.for about 30 minutes, before being unmolded to yield the final lipstickproduct. Percents (by weight) of the components of the compositionreaction mixture are indicated in Table 10.

TABLE 10 Component Weight percent ETPEA 25 2-Octyldodecanol 10 Pigments5 Polyamide fiber (3 mm long, 0.9 Dtex) 0 to 10 Hydrogenated isoparaffin(Parleam) q.s. 100

Example 11 Anhydrous Cast Foundations

In one aspect, the present invention provides a composition in the formof an anhydrous cast foundation, prepared, for example, in a mannersimilar to that of Example 10, according to the weight percentage valuesindicated in Table 11. The presence of fiber reduces the extent to whichthe composition exudes oil at its surface. The isododecane contributesto the non-transfer properties of the composition.

TABLE 11 Component Weight percent ETPEA 25 Isododecane 15 Pigments 8Polyamide fiber (3 mm long, 0.9 Dtex) 0 to 10 Hydrogenated isoparaffin(Parleam) q.s. 100

Example 12 Anhydrous Foundation

In one aspect, the present invention provides a composition in the formof an anhydrous foundation, prepared, for example, in a manner similarto that of Example 10, according to the weight percentage valuesindicated in Table 12.

TABLE 12 Component Weight percent ETPEA 11 Parleam 10 Pigments 10Polyamide fiber (3 mm long, 0.9 Dtex) 5 Isododecane q.s. 100

Example 13 Eye Shadow

In one aspect, the present invention provides a composition in the formof an eye shadow prepared, for example, in a manner similar to that ofExample 10, according to the weight percentage values indicated in Table13. In one aspect, the increased presence of fibers, optionally combinedwith fillers, improves the transfer-resistance property compared with acomposition not containing any fibers. In a further aspect, thecombination of spherical fillers with fibers improves the disintegrationof the product and thus makes it easier for the make-up to be depositedon the skin.

TABLE 13 Component Weight percent ETPEA 11 Parleam 10 Blue 1 Al lake 0.1Polyamide fiber (3 mm long, 0.9 Dtex) 0 to 5 Nylon-12 powder (sphericalfiller) 0 to 10 Isododecane q.s. 100

Example 14 Nail Polish

In one aspect, the present invention provides a composition in the formof a nail polish, prepared by reacting together the ingredientsindicated in Table 14. In a preferred aspect, the nail polish product isprovided in the form of a structured solid composition, such as a stick.

TABLE 14 Component Weight percent ETPEA 20 Nitrocellulose 8 Pigments 1Butyl acetate q.s. 100

Example 15 Transfer Resistant Mascara

In one aspect, the present invention provides a composition in the formof a transfer resistant mascara, prepared by reacting together theingredients indicated in Table 15, as follows. Phases A, B, and C areeach prepared separately by mixing together the ingredients of eachphase. The three phases are then combined and in a preferred aspect themascara composition has transfer resistant properties upon applicationto eyelashes.

TABLE 15 Phase Component Weight percent A Isododecane 41.97 Alkylsilicone resin with alkyl groups (MK Resin) 7.00 Isododecane gel(VERSAGEL ™ MD 870) 16.50 Quaternium 18 Hectorite 4.00 Black iron oxide5.00 B Propylene carbonate 1.32 C Paraffin 3.00 Carnauba wax 5.20Beeswax 7.00 Synthetic beeswax 4.00 ETPEA 5.00 Phenoxyethanol 0.01

Example 16 Transfer Resistant Mascara

In one aspect, the present invention provides a composition in the formof a transfer resistant mascara, prepared by reacting together theingredients indicated in Table 16. In one aspect, Phase A is mixed witha homogenizer for 20 minutes at ambient temperature and then heated toabout 65° C. for about 15 minutes. In a separate vessel, the componentsof phase C are combined with propeller mixing and heated to about 85-90°C., before adding phase C to phase A. After homogenizing the mixture forabout 5 minutes while maintaining the heat at about 80-85° C., phase Bcan then be added to the mixture. The mixture can then be furtherhomogenized for about 30 minutes at about 80-85° C. before being cooledto about 30-35° C. using sweep mixing. Preferably, the resulting mascaracomposition has transfer resistant properties upon application toeyelashes.

TABLE 16 Phase Component Weight percent A Isododecane 40.4Trimethylsiloxysilicate 7.0 Isododecane with 14.0 a)Styrene-ethylene/butylene-styrene 1.2 triblock copolymer, and b)Styrene-ethylene/propylene radial 1.2 copolymer Distearyldiammoniumhectorite 5.5 Iron oxides 5.0 B Propylene carbonate 1.8 C Allylstearate/VA copolymer 5.0 Waxes 16.8 Preservatives 0.01 ETPEA 5.00

Example 17 Anhydrous Compact Foundation

In one aspect, the present invention provides a composition in the formof an anhydrous compact foundation prepared, for example, in thefollowing manner. ETPEA is solubilized at about 100° C., in a mixture ofmelted oils and wax, followed by addition of pigments and fillers. Themixture can then be further mixed using, for example, a deflocculatingturbomixer (Raynerie). Preferably the resulting composition has goodstability (as indicated by, for example, the absence of exudation atambient temperature, 45° C., and 47° C., both after one month and aftertwo months. Percents (by weight) of the components of the compositionreaction mixture are indicated in Table 17. This compositionillustrates, e.g., the use of a solid substance in a composition of thepresent invention.

TABLE 17 Component Weight percent Octyldodecanol 4.4 PTFE 4.0 Polymethylmethacrylate 4.0 ETPEA 7.5 Polyethylene wax MW 500 5.7 (weight averagemolecular weight) Titanium dioxide treated with dimethicone 5.0 Kaolin3.0 Talc 8.3 Methylparaben 0.2 Titanium dioxide anatase form 10.6 Ironoxides 3.4 Isononyl isononanoate 15.0 Isostearyl neopentanoate q.s.100.0

Example 18 Lipstick

In one aspect, the present invention provides a composition in the formof a lipstick prepared, for example, in the following manner. ETPEA issolubilized at about 100° C., in a mixture of melted oils and wax,followed by addition of pigments and fillers. The mixture can then befurther mixed using, for example, a deflocculating turbomixer(Raynerie), before being encased in lipstick molds. Preferably theresulting composition has good stability (as indicated by, for example,the absence of exudation at ambient temperature, 45° C., and 47° C.,both after one month and after two months. Percents (by weight) of thecomponents of the composition reaction mixture are indicated in Table18. This composition illustrates, e.g., the use of a solid substance ina composition of the present invention.

TABLE 18 Component Weight percent Rosin/Colophonium 0.6 Barium sulfate0.6 Titanium dioxide 1.2 Red 7 Lake 1.8 Nylon-12 4.0 Iron oxides 4.0Polyglyceryl-2 diisostearate 5.9 Polyethylene wax 12.0 Diisostearylmalate 12.0 ETPEA 15.0 Isononyl isononanoate q.s. 100.0

Example 19 Lipstick

In one aspect, the present invention provides a composition in the formof a lipstick, prepared by reacting together the ingredients indicatedin Table 19. In one aspect, the lipstick composition is prepared asfollows. First, silica gel (phase B) is prepared by charging a reactionvessel with hydrogenated polyisobutene and octyldodecanol, then addingsilica gel portionwise to the mixture, with stirring, in a Rayneristirrer at about 60° C. In a separate reaction vessel, ground pigmentarymaterial (phase C) can be prepared by first charging the reaction vesselwith lanolin, hydrogenated poly isobutene, and octyldodecanol, heatingthe mixture to about 60° C., mixing pigment into the mixture, thengrinding the mixture (for example, about three times in a three-rollmill). Phases B and C can then be combined, heated to about 100° C., andhomogenized with stirring.

ETPEA and the oils of phase A can then be introduced into a separateheating vessel. The mixture of phase A can then be placed under magneticstirring and then heated in a first stage to about 100° C. (or at suchtemperature warm enough to liquefy the ETPEA). The mixture containingphases B and C can then be introduced to the heating vessel. Theresulting product can then be placed in a heated mold (about 45° C.)with stirring and, once setting begins, can then be placed in a freezer(about −21° C.) for about 15 minutes.

The hardness of the lipstick may be measured using the “cheese wire”test described herein. The fragility of the composition may bedetermined by a method such as wherein the stick is submitted to severalback-and-forth movements on a support for about 3 minutes at a speed ofabout 60 back-and-forth movements per minute, at about 20° C., with theindex of fragility defined as that percentage of sticks that break uponundergoing the test conditions. This composition illustrates, e.g., theuse of a solid substance in a composition of the present invention.

TABLE 19 Phase Component Weight percent A ETPEA 16.00 Carnauba wax 13.00Isononyl isonononanoate 13.00 Diisostearylmalate 9.00 B Hydrophobicsilica 3.00 Hydrogenated polyisobutene 10.36 Octyldodecanol 3.52 CPigments 12.00 Liquid lanolin 14.00 Hydrogenated poly isobutene 4.64Octyldodecanol 1.48

Example 20 Lipstick

In one aspect, the present invention provides a composition in the formof a lipstick, prepared by reacting together the ingredients indicatedin Table 20. In one aspect, the lipstick composition is prepared asfollows. First, silica gel (phase B) is prepared by charging a reactionvessel with hydrogenated polybutene and isononyl isononanoate, thenadding silica gel portionwise to the mixture, with stirring, in aRayneri stirrer at about 60° C. In a separate reaction vessel, groundpigmentary material (phase C) can be prepared by first charging thereaction vessel with hydrogenated polybutene, heating the mixture toabout 60° C., mixing pigment into the mixture, then grinding the mixture(for example, about three times in a three-roll mill). In one aspect,phases B and C can then be combined, heated to about 100° C., andhomogenized with stirring.

ETPEA and the oils of phase A can then be introduced into a separateheating vessel. The mixture of phase A can then be placed under magneticstirring and then heated in a first stage to about 100° C. (or at suchtemperature warm enough to liquefy the ETPEA). The mixture containingphases B and C can then be introduced to the heating vessel. In oneaspect, the whole mixture can then be mixed using, for example, adeflocculating turbomixer (Raynerie) with stirring for about 90 minutes.The resulting product can then be placed in a mold (optionally heated toabout 45° C.) with stirring and, once setting begins, can optionally beplaced in a freezer (about −21° C.) for about 15 minutes.

In one aspect the sticks of lipstick have a diameter of about 8-13 mm.The hardness of the stick may be measured using the “cheese wire” testdescribed herein. Preferably the lipsticks of the present invention havegood staying power, and are glossy and non-greasy. Also preferably thelipsticks of the present invention are stable and do not exude atambient temperature or at about 47° C., for about 2 months. These sticksillustrate, e.g., the use of at least one inert filler in a compositionof the present invention.

TABLE 20 Phase Component Weight percent A ETPEA 18 Diisononylisononanoate 5 Diisostearylmalate 17 Hydrogenated polybutene (Parleam) 4B Hydrophobic silica (Aerosil R972) 3 Hydrogenated polybutene 25Isononyl isononanoate 12 C Pigments 7 Hydrogenated polybutene 9

Examples 21-23 Cast Foundations

In one aspect, the present invention provides a composition in the formof a cast foundation, prepared by reacting together the ingredientsindicated in Table 21. In one aspect, the cast foundation composition isprepared as follows. A heating vessel is charged with ETPEA and isononylisononanoate, the mixture is heated to 110° C., and stirred with aRayneri mixer for about 10 minutes, until the ETPEA has fully dissolved.This mixture can be designated “Phase A.”

In parallel, a pigmentary phase can be prepared by incorporatingpigments (for example, iron oxide+titanium oxide) into isododecane,followed by milling using a three-roll mill. This pigmentary phase(“Phase B”) can then be introduced into phase A and the mixture can bestirred until completely homogeneous, in one aspect for about 30 minutesat about 110° C. The temperature of the mixture can then be lowered toabout 95° C., before adding isododecane (“Phase D”) to the mixture.After stirring the resulting mixture for about 15 minutes, the filler(“Phase C”) can be incorporated with stirring for about 20 minutes more.The final mixture can then be cast in foundation molds (in one aspectpreheated to about 45° C.), and the mixture can be left to cool toambient temperature. Preferably, the composition exhibits good stability(i.e., no phase separation) at about 4° C., ambient temperature, andabout 45° C., over a length of time spanning about one month, and morepreferably about two months. Also preferably, the composition is easy tospread and has a pleasant, non-greasy, light and fondant feel on thefingers. The composition also preferably provides a homogeneous, smooth,natural, and light make-up effect. These sticks illustrate, e.g., theuse of at least one inert filler in a composition of the presentinvention.

TABLE 21 Weight percent Phase Component Ex. 21 Ex. 22 Ex. 23 A ETPEA 1111 11 Isononyl isononanoate 10 10 10 B Coated yellow iron oxide* 2.2 2.22.2 Coated red iron oxide* 0.5 0.5 0.5 Coated black iron oxide* 0.3 0.30.3 Titanium oxide* 7.0 7.0 7.0 C Silica beads (Tospearl 145A) 10 — —Nylon particles — 10 — PMMA particles (10 to 12 μm, — — 10 WackherrCOVABEAD ® LH-85) D Isododecane q.s. q.s. q.s. 100.0 100.0 100.0 *Thecoating is aluminum stearoylglutamate.

Example 24 Cast Foundation

In one aspect, the present invention provides a composition in the formof a cast foundation, prepared by reacting together the ingredientsindicated in Table 22 in a manner similar to that described in EXAMPLES21-23. In one aspect, the cast foundation composition has the samecosmetic properties as those of EXAMPLES 21-23. These sticks illustrate,e.g., the use of at least one inert filler in a composition of thepresent invention.

TABLE 22 Component Weight percent Octyldodecanol 4.4Polytetrafluoroethylene wax 4.0 (particle size 8 μm, MW: 75,000*) Hollowpolymethyl methacrylate microspheres 4.0 (particle size: 10 to 12 μm)ETPEA 7.4 Polyethylene wax MW: 500* 3.7 Nano-titanium oxide (particlesize 2 nm) 5.0 coated with PDMS Kaolinite (hydrated aluminum silicate)3.0 Talc (particle size 2 μm) 8.3 Methyl p-hydroxybenzoate 0.2 Titaniumoxide (untreated anatase) 10.6 Black iron oxide 1.0 Yellow iron oxide2.1 Isononyl isononanoate 15.0 Isostearyl neopentanoate q.s. 100.0 *MW:number-average molecular mass.

Example 25 Mascara

In one aspect, the present invention provides a composition in the formof a mascara, prepared by mixing the ingredients as indicated in Table23. In a preferred aspect, the mascara obtained is easy to apply,adheres well to the eyelashes during and after application, and allowsthe eyelashes to be made up quickly.

TABLE 23 Component Weight percent ETPEA 1.0 Carnauba wax 2.6 Beeswax 3.3Paraffin wax 10.4 Hydrogenated jojoba oil 0.2 Hydrogenated palm oil 0.22-Amino-2-methyl-1,3-propanediol 0.8 Triethanolamine 2.4 Stearic acid6.6 Hydroxyethylcellulose 0.8 Gum arabic 0.6 Ethyl acrylate/methylmethacrylate copolymer 5.0 AM (80/20) as an aqueous dispersioncontaining 50% AM (Daitosol 5000 AD from Saito) Black iron oxide 7.0Preserving agents q.s. Water q.s. 100.0

Example 26 Mascara

In one aspect, the present invention provides a composition in the formof a mascara, prepared by mixing the ingredients as indicated in Table24. In a preferred aspect, the mascara obtained adheres well to theeyelashes during and after application, gives the eyelashesinstantaneous loading, and allows the eyelashes to be made up quickly.

TABLE 24 Component Weight percent ETPEA 1.0 Carnauba wax 4.6 Rice branwax 2.1 Beeswax 8.2 Paraffin 2.2 Talc 1.0 Bentonite 5.0 Vinylacetate/allyl stearate copolymer (65/35) 6.5 (MEXOMER ™ PQ from Chimex)Polyvinyl laurate (MEXOMER ™ PP from 0.7 Chimex) Sulfopolyester (AQ 55Sfrom Eastman 0.12 Chemical) Isododecane 53.9 Propylene carbonate 1.6Pigments 4.9 Preserving agents q.s. Water q.s. 100.0

Examples 27-39 Clear Anhydrous Sunscreen Stick (Opitionally With anOil-Soluble Cationic Polymer)

In one aspect, the present invention provides a composition in the formof a clear anhydrous sunscreen stick, prepared by reacting together theingredients indicated in Table 25. In one aspect, the sunscreen stickcomposition is prepared as follows. The ingredients of phase A are addedto a main vessel and heated to about 110° C.-115° C. while mixing withthe aid of an impeller mixer. Then phase B is added to phase A withcontinued mixing. ETPEA from phase B is allowed to dissolve, and themixture is then cooled to about 80° C.-82° C. Phases C, D, and E arethen added to the mixture while maintaining the temperature at about 80°C.-82° C. with slow impeller mixing. Compositions are mixed untilhomogenous (in one aspect, about one minute), then are used to fill asuitable container or mold.

In certain aspects, the resulting compositions acquire a fine tomoderate uniform oil coat covering the composition surface. Preferably,the resulting compositions are firm at ambient temperature, while theoverall structure and stick characteristics remain unchanged when thetemperature is elevated to about 45° C.

The compositions of these examples illustrate, e.g., a personal careproduct comprising ETPEA as a structuring polymer, and at least twocomponents selected from (a) at least one oil-soluble ester comprisingat least one free hydroxy group; (b) at least one oil-soluble cationicsurfactant; and (c) at least one oil-soluble polymer chosen from alkylcelluloses and alkylated guar gums. The compositions may be, e.g., inthe form of a fluid anhydrous gel, a rigid anhydrous gel, a fluid simpleemulsion, a rigid simple emulsion, a fluid multiple emulsion, and arigid multiple emulsion. The composition may contain at least one oil,such as a polar oil or an apolar oil. The composition may contain atleast one non-volatile oil. The composition may contain at least onesalt of a fatty amine. Examples of oil-soluble esters comprising atleast one free hydroxy group include propylene glycol ricinoleate,isopropyl hydroxystearate, triisocetyl citrate, diisostearyl malate,octyl hydroxystearate, triisoarachidyl citrate, cetyl lactate, dioctylmalate, octyldodecyl hydroxystearate, di-isostearyl malate, anddi-isostearyl lactate. The composition may include a fatty alcohol,e.g., a C8-C26 fatty alcohol.

TABLE 25 Weight percent Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex.Ex. Phase Component 27 28 29 30 31 32 33 34 35 36 37 38 39 ADiisostearyl 11.1 11.1 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.010.0 malate Dioctyl malate 11.1 11.1 20.0 20.0 20.0 20.0 20.0 20.0 20.020.0 20.0 20.0 20.0 Castor oil 36.7 36.6 30.6 29.9 29.0 28.9 27.9 29.426.15 24.15 22.9 23.9 23.15 Propylene glycol 11.7 11.7 10.5 10.5 10.510.5 10.5 10.5 10.5 10.5 10.5 10.5 10.5 ricinoleate Lauryl methyl — — —— — 1.0 2.0 0.5 — — — — — glyceth-10 hydroxypropyl diammonium chlorideN-Hance-AG-50 — — — — — — — — — 2.0 — — — (C₁–C₅ alkyl galactomannan)N-Hance-AG-200 — — — — — — — — — — 3.0 — — (C₁–C₅ alkyl galactomannan)Ethocell 100 — — — — — — — — — — — 2.0 — (Ethyl cellulose) Ethocell 7 —— — — — — — — — — — — 3.0 (Ethyl cellulose) B ETPEA 17.8 17.8 16.0 16.016.0 16.0 16.0 16.0 16.0 16.0 16.0 16.0 16.0 C Cetyl alcohol — — 2.0 3.04.0 3.0 3.0 3.0 4.0 4.0 4.0 4.0 4.0 Propyl parraben — — — — — 0.1 .0.10.1 0.1 0.1 0.1 0.1 0.1 D Benzo- 3.3 3.3 3.0 3.0 3.0 3.0 3.0 3.0 — — — —— phenone-3 Octyl methoxy- 8.3 8.3 7.5 7.5 7.5 7.5 7.5 7.5 — — — — —cinnamate Butyl methoxy- — — — — — — — — 3.0 3.0 3.0 3.0 3.0 dibenzoylmethane Octocrylene — — — — — — — — 10.0 10.0 10.0 10.0 10.0 E Others* —0.06 0.4 0.1 — — — — 0.25 0.25 0.5 0.5 0.25 *Others: preservatives,masking agents, colorants, vitamins, oil-soluble actives, antioxidants,dermatological actives, flavoring oils, etc.

Example 40-41 Lipsticks With an Oil-Soluble Cationic Polymer

In one aspect, the present invention provides a composition in the formof a lipstick with an oil-soluble cationic polymer and/or an oil-solubleester, prepared, for example, by mixing the ingredients as indicated inTable 26. In one aspect, the composition is mixed until homogeneous,then poured into a suitable container or mold. Preferably thecompositions have good stability and no exudation, even at elevatedtemperatures such as about 47° C.

TABLE 26 Weight percent Component Ex. 40 Ex. 41 Hydroxyhydrocinnamate0.05 0.05 Rosin/Colophonium tetradibutyl pentaerythrityl 0.6 0.6 Bariumsulfate 0.6 0.6 Titanium dioxide 1.2 1.2 Red 7 Lake 1.8 1.8 Nylon-12 3.04.0 Iron oxides 4.0 4.0 Polyethylene 3.0 12.0 ETPEA 15.0 15.0Polyglycerol-2 diisostearate 5.9 5.9 Octyldodecanol 10.0 — Isononylisononanoate 5.9 q.s. 100.0 Diisostearyl malate q.s. 100.0 12.0

Examples 42-44 Anhydrous Gel Lip Compositions

In one aspect, the present invention provides a composition in the formof an anhydrous gel lip composition prepared, for example, by mixing theingredients as indicated in Table 27. In one aspect, the composition ismixed until homogeneous, then poured into a suitable container or mold.Preferably the compositions have good stability at ambient temperature,as well as good sunscreen properties.

TABLE 27 Weight percent Component Ex. 42 Ex. 43 Ex. 44 ETPEA 25.0 25.025.0 Hydrogenated polyisobutene 62.0 58.0 55.5 Octyldodecanol 10.0 10.010.0 Hydrogenated polyisobutene (45%) 0.01 0.01 0.01 Polyhydroxystearicacid (5%) Yellow 5 Lake (50%) Ethylhexyl methoxycinnamate 1.0 5.0 7.5Fragrance 2.0 2.0 2.0

Example 45 Lipstick

In one aspect, the present invention provides a composition in the formof a lipstick, prepared by reacting together the ingredients indicatedin Table 28. In one aspect, the lipstick composition can be prepared asfollows. First, silica (phase B) is charged to a heating vessel and thendispersed using a Rayneri stirrer in the mixtures of oils of phase B,heated to about 60° C. When the resulting gel is homogeneous, Bentonecan then be added. The mixture can then be stirred until a homogeneouspreparation is obtained, corresponding to phase B. Phase C can beprepared by grinding pigment in hydrogenated polybutene using, forexample, a three-roll mill.

ETPEA (phase A) can then be added to phase B and the mixture can beheated to about 100° C. When the resulting mixture becomes homogeneous,the ground material C can then be added, and the resulting mixture canthen be heated for about 90 minutes with stirring. The preparation canthen be discharged into molds for lipsticks in stick form.

In one aspect, the produced sticks of lipstick have a diameter of about8.1 mm. In preferred aspects, the sticks of lipstick do not exude atambient temperature for several months, and at about 37° C. or 47° C.for about one month; and the sticks deposit a glossy film with goodstaying power and no migration. The composition of this exampleillustrates the inclusion of a gelling agent (in this case, Bentone 38V,a modified clay) in a personal care composition.

TABLE 28 Phase Component Weight percent A ETPEA 18.0 B Bentone 38V 3.0Diisostearyl malate 16.3 Isononyl isononanoate 2.3 Hydrogenatedpolybutene 36.4 Hydrophobic silica 3.0 (Aerosil R972) C Pigments 7.0Isononyl isononanoate 14.0

Example 46 Lipstick

In one aspect, the present invention provides a composition in the formof a lipstick, prepared by reacting together the ingredients indicatedin Table 29. In one aspect, the lipstick composition can be prepared asfollows. First, ETPEA, GP-1, and the oils of phase A can be introducedinto a heating vessel. The mixture can then be placed under magneticstirring and heated in a first stage to about 100° C. (or at suchtemperature warm enough to liquefy the ETPEA), then to a temperaturerequired to obtain a transparent homogeneous liquid. The mixture canthen be heated to a temperature about 10° C. above that which isrequired to obtain a transparent homogeneous liquid; before beingcombined with a mixture comprising phases B and C (prepared according toEXAMPLE 20). The whole mixture can then be stirred for about 1 hourbefore being cast in a mold (optionally heated to about 45° C. Once thecomposition begins to set, the charged mold can then be optionallyplaced in a freezer (about −21° C.) for about 15 minutes. In one aspect,the sticks of lipstick composition have a diameter of about 12.7 mm Thehardness of the composition may be measured (for example) with a “cheesewire.” Preferably the sticks of the lipstick composition of the presentinvention do not break during measurement of dynamic fragility.

The composition of this Example illustrates a composition of the presentinvention comprising an organogelator. Organogelators as a group aredefined, e.g., in PCT International Publication No. WO 02/055030, thedisclosure of which is incorporated herein by reference.

TABLE 29 Phase Component Weight percent A ETPEA 18.0 GP-1 (fromAjinomoto) 5.0 Isononyl isononanoate 3.3 Diisostearyl malate 15.3Hydrogenated polybutene 2.3 (Parleam) B Hydrophobic silica 3.0Hydrogenated polybutene 25.0 (Parleam) Isononyl isononanoate 12.0 CPigments 7.0 Hydrogenated polybutene 9.0 (Parleam)

Example 47 Lipstick

In one aspect, the present invention provides a composition in the formof a lipstick, prepared by reacting together the ingredients indicatedin Table 30. In one aspect, the lipstick composition can be prepared asfollows. First, ETPEA, trans-diaminocyclohexane derivative, and the oilsof phase A can be introduced into a heating vessel. The mixture can thenbe placed under magnetic stirring and heated in a first stage to about100° C. (or at such temperature warm enough to liquefy the ETPEA), thento a temperature required to obtain a transparent homogeneous liquid.The mixture can then be heated to a temperature about 10° C. above thatwhich is required to obtain a transparent homogeneous liquid; beforebeing combined with a mixture comprising phases B and C (preparedaccording to EXAMPLE 20). The whole mixture can then be stirred forabout 1 hour before being cast in a mold (optionally heated to about 45°C. Once the composition begins to set, the charged mold can then beoptionally placed in a freezer (about −21° C.) for about 15 minutes. Inone aspect, the sticks of lipstick composition have a diameter of about12.7 mm and a hardness that can be measured (for example) with a “cheesewire.” In preferred aspects, the sticks of the lipstick composition ofthe present invention do not break during measurement of dynamicfragility; the sticks of the lipstick composition do not exude; and thesticks of the lipstick composition deposit a glossy make-up on the lips.The composition of this Example illustrates a composition of the presentinvention comprising an organogelator. Organogelators as a group aredefined, e.g., in PCT International Publication No. WO 02/055030, thedisclosure of which is incorporated herein by reference.

TABLE 30 Phase Component Weight percent A ETPEA 18.0Trans-N,N′=bis(dodecanoyl)- 5.0 1,2-diaminocyclohexane Isononylisononanoate 3.3 Diisostearyl malate 15.3 Hydrogenated polybutene 2.3(Parleam) B Hydrophobic fumed silica 3.0 Hydrogenated polybutene 25.0(Parleam) Isononyl isononanoate 12.0 C Pigments 7.0 Hydrogenatedpolybutene 9.0 (Parleam)

Examples 48-49 Lipstick

In one aspect, the present invention provides a composition in the formof a lipstick, prepared by reacting together the ingredients indicatedin Table 31. In one aspect, the lipstick composition can be prepared asfollows. First, phase A can be introduced into a heating vessel, placedunder magnetic stirring and heated to a temperature required to obtain atransparent homogeneous liquid. The mixture can then be heated to atemperature about 10° C. above that which is required to obtain atransparent homogeneous liquid, before being combined with pigmentsground in a three-roll mill (phase B) followed by phase C. The wholemixture can then be stirred for about 90 minutes before being cast in amold (optionally heated to about 45° C. Once the composition begins toset, the charged mold can then be optionally placed in a freezer (about−21° C.) to carry out tempering. In one aspect, the sticks of lipstickcomposition have a diameter of about 12.7 mm and a hardness of about 150to 204 gf, measured (for example) with a “cheese wire.” In preferredaspects, the sticks of the lipstick composition of the present inventiondo not break during measurement of dynamic fragility; do not exude; andare glossy in appearance; and the deposit on the lips from the sticks ofthe lipstick composition is comfortable and glossy.

The composition of this Example illustrates a composition of the presentinvention comprising an organogelator. Organogelators as a group aredefined, e.g., in PCT International Publication No. WO 02/055030, thedisclosure of which is incorporated herein by reference.

TABLE 31 Weight percent Phase Component Ex. 48 Ex. 49 A ETPEA 18.0018.00 GP-1 (Ajinomoto) 5.00 — Trans-N,N′=bis(dodecanoyl)- — 5.001,2-diaminocyclohexane Polyethylene wax MW: 500* 3.00 3.00 Liquidlanolin 5.00 5.00 BHT 0.07 0.07 Octyl dodecanol 8.25 8.25 Phenylsilicone 4.58 4.58 (20 cSt at 25° C.) Hydrogenated polybutene 22.2422.24 (Parleam) B POLYTRAP ® 3.00 3.00 (Dow Corning) Hydrogenatedpolybutene 20.00 20.00 (Parleam) Pigments 8.66 8.66 C Fragrance 0.200.20

Example 50 Scenting Composition

In one aspect, the present invention provides a composition in the formof a lipstick, prepared by reacting together the ingredients indicatedin Table 32. In one aspect, the lipstick composition can be prepared asfollows. The constituents, except for the perfume extract, can be mixedunder hot conditions (e.g., about 80° C.) and the perfume extract issubsequently added. The mixture can then be stirred, and then cast whilecooling to ambient temperature. In preferred aspects, the resultingproduct is a visually perfect transparent stick; and the product ishighly scenting, the fragrance persisting for a long time afterapplication to the skin.

TABLE 32 Component Weight percent ETPEA 25 Perfume extract 4 Perfume oil61 Octyldodecanol 10

Example 51 Balm for the Lips Scented With Violet

In one aspect, the present invention provides a composition in the formof a balm for the lips scented with violet, prepared by reactingtogether the ingredients indicated in Table 33. In one aspect, thelipstick composition can be prepared in a manner similar to thatdescribed in EXAMPLE 50. In preferred aspects, the resulting product istransparent; the resulting product is violet in color; and the resultingproduct pleasantly scents the lips.

TABLE 33 Component Weight percent ETPEA 25 “Violine” fragrance 4 Parleamoil 60.998 Octyldodecanol 10 D&C Violet No. 2 dye 0.002

Example 52 Scenting Stick

In one aspect, the present invention provides a composition in the formof a scenting stick, prepared by reacting together the ingredientsindicated in Table 34. In one aspect, the lipstick composition can beprepared in a manner similar to that described in EXAMPLE 50. In apreferred aspect, the resulting product is transparent.

TABLE 34 Component Weight percent ETPEA 25 Fragrance 2 Octyldodecanol 73

Example 53 Scenting Cast Product

In one aspect, the present invention provides a composition in the formof a scenting cast product, prepared by reacting together theingredients indicated in Table 35. In one aspect, the lipstickcomposition can be prepared in a manner similar to that described inEXAMPLE 50.

TABLE 35 Component Weight percent ETPEA 25 Fragrance 2 Octyldodecanol 73

Example 54 Scenting Cast Product

In one aspect, the present invention provides a composition in the formof a scenting cast product, prepared by reacting together theingredients indicated in Table 36. In one aspect, the lipstickcomposition can be prepared in a manner similar to that described inEXAMPLE 50.

TABLE 36 Component Weight percent ETPEA 20 Fragrance 2 Octyldodecanol 78

Examples 55-56 Foundation

In one aspect, the present invention provides a composition in the formof cosmetic foundation, prepared by reacting together the ingredientsindicated in Table 37. In one aspect, the cosmetic foundationcomposition can be prepared as follows. First, a reaction vessel ischarged with phase B, and the reaction mixture can be heated to about120° C., optionally with agitation, then homogenized, for example, witha deflocculating turbomixer (Raynerie). The reaction can then be furthercharged with phase A, followed by pigments ground in a three-roll mill(phase C), and the resulting mixture is brought to about 100° C. Thereaction vessel can then be further charged with phase D and phase E ina gradual steady manner, with the aid of a homogenizer. The reactionmixture is allowed to react for about 10 minutes before being dischargedinto product containers.

In various aspects, the resulting product is solid, held easily on afinger, and has a hardness strength of about 35 to 50 g. In anotheraspect the cosmetic foundation composition is moist and preferablyspreads out well, forming a uniform, light deposit on the skin. In apreferred aspect, the resulting cosmetic product is natural and satiny.

TABLE 37 Weight percent Phase Component Ex. 55 Ex. 56 A Sorbitanisostearate 4.50 4.50 (Uniqema ARLACEL ™ 987) Preservative 0.20 0.20 BETPEA 15.00 17.00 Octyl-2-dodecanol 3.60 3.60 Hydrogenated isoparaffin(Parleam) 11.00 11.00 C Titanium dioxide 4.10 4.10 Hydrogenatedisoparaffin (Parleam) 7.00 7.00 Iron oxide 1.30 1.30 D Perfume 0.65 0.65E Propylene glycol 3.00 3.00 Magnesium sulfate 0.70 0.70 Preservative0.30 0.30 Water q.s. 100.00 q.s. 100.00

Example 57 Solid Foundation

In one aspect, the present invention provides a composition in the formof solid cosmetic foundation, prepared by reacting together theingredients indicated in Table 38. In one aspect, the cosmeticfoundation composition can be prepared in a manner similar to thatdescribed in EXAMPLES 55-56. In one aspect, the resulting product has anice solid texture and exhibits properties similar to those of theproduct composition of EXAMPLES 55-56.

TABLE 38 Phase Component Weight percent A Sorbitan isostearate 4.50(Uniqema ARLACEL ™ 987) Preservative 0.20 B ETPEA 15.00Octyl-2-dodecanol 3.60 Isododecane 5.00 Hydrogenated isoparaffin(Parleam) 6.00 C Titanium dioxide 4.10 Hydrogenated isoparaffin(Parleam) 7.00 Nylon powder 8.00 Iron oxide 1.30 D Perfume 0.65 EPropylene glycol 3.00 Magnesium sulfate 0.70 Preservative 0.30 Waterq.s. 100.00

Example 58 Foundation

In one aspect, the present invention provides a composition in the formof solid cosmetic foundation, prepared by reacting together theingredients indicated in Table 39. In one aspect, the cosmeticfoundation composition can be prepared in a manner similar to thatdescribed in EXAMPLES 55-56. In one aspect, the resulting product has afine solid texture and exhibits properties similar to those of theproduct composition of EXAMPLES 55-56.

TABLE 39 Phase Component Weight percent A Sorbitan isostearate 6.00(Uniqema ARLACEL ™ 987) Preservative 0.20 B ETPEA 15.00Octyl-2-dodecanol 3.60 Isododecane 22.50 Cyclohexadimethylsiloxane (8cSt) 5.00 (Dow Corning DC246) Hydrogenated isoparaffin (Parleam) 11.00 CTitanium dioxide 4.10 Hydrogenated isoparaffin (Parleam) 3.30 Nylonpowder 4.00 Iron oxide 10.70 D Perfume 0.65 E Magnesium sulfate 0.70Preservative 0.20 Water q.s. 100.00

Examples 59-60 Lipstick

In one aspect, the present invention provides a composition in the formof lipstick, prepared by reacting together the ingredients indicated inTable 40. In one aspect, the lipstick composition can be prepared asfollows. First, the pigmentary phase (B) is ground with the aid of athree-roll mill, and is then introduced into the oily phase A. Thismixture can then be heated to about 100° C., optionally with stirring,until homogeneous. The temperature of the mixture can then be reduced toabout 85° C. before adding volatile phase C. The whole reaction mixturecan then be allowed to react for about 10 minutes before discharginginto lipstick molds. In one aspect, the resulting lipstick compositiondeposits a glossy and non-transferable film.

TABLE 40 Weight percent Phase Component Ex. 59 Ex. 60 A ETPEA 18 18Castor oil 7 8 Hydrogenated isoparaffin 4 5 Isononyl isononanoate 4 5Phenyl trimethylsiloxy trisiloxane 8 8 Copolymervinylpyrrolidone/1-eicosene 2 2 B Pigments 10 10 Hydrogenatedisoparaffin 5 5 liquid lanolin 5 5 Poly(12-hydroxystearic) acid 2 2 CIsododecane 25 27 Decamethyl tetrasiloxane 10 5

Example 61 Lipstick

In reference to Table 41, the pigmentary phase (B), ground with the aidof a three-roll mill, is introduced into the oily phase A (heated toabout 100° C. prior to mixing), and the mixture is allowed to reactuntil completely homogeneous. After reducing the heat of the reactionmixture to about 85° C., the volatile phase C can then be added to themixture. The resulting reaction mixture is then allowed to react forabout 10 minutes before being poured into lipstick molds, affording astick bi-product. In one aspect the bi-product is a stick with two tipswhich presents two options: one tip is glossy in color and can deposit aglossy colored film on the lips, while a second tip can deposit on thelips a film with reduced cling and reduced transferability. Preferably,the stick does not exude at ambient temperature for a period lasting atleast about 2 months.

In one aspect, the stick product essentially provides 3 different typesof lipstick to the user: 1) a single-coat lipstick with reducedtransferability, 2) a glossy single-coat lipstick, and 3) a double-coatlipstick containing the properties of lipstick types 1 and 2. In oneaspect of the double-coat lipstick, the base coat (i.e., the coat indirect contact with the lips) is the coat with reduced transferability,while the superior coat (i.e., the coat applied over the base coat) isthe glossy coat. In another aspect of the double-coat lipstick, the twocoats are applied in the order reverse to the foregoing. In otheraspects, the resulting makeup is comfortable, non-clinging, glossy, andof high quality.

TABLE 41 Phase Component Weight percent A ETPEA 18 Fluorinated silicone(Shin Etsu X22819) 5 Castor oil 2 Hydrogenated isoparaffin 4 Isononylisononanoate 4 Phenyl trimethylsiloxytrisiloxane 8 Copolymervinylpyrrolidone/1-eicosene 2 B Pigments (iron oxide) 10 Hydrogenatedisoparaffin 5 Liquid lanolin 5 Poly(12-hydroxystearic) acid 2 (AveciaSOLSPERSE ™ 21 000) C Isododecane 25 Decamethyltetrasiloxane 10

Example 62 Lipstick

In reference to Table 42, the pigmentary phase (B), ground with the aidof a three-roll mill, is introduced into the oily phase A (heated toabout 100° C. prior to mixing), and the mixture is allowed to reactuntil completely homogeneous. After reducing the heat of the reactionmixture to about 85° C., the volatile phase C can then be added to themixture. The resulting reaction mixture is then allowed to react forabout 10 minutes before being poured into lipstick molds, affording astick bi-product. In one aspect the bi-product is a stick with two tipswhich presents two options: one tip is glossy in color and can deposit aglossy colored film on the lips, while a second tip can deposit on thelips a film with reduced cling and reduced transferability. Preferably,the stick does not exude at ambient temperature for a period lasting atleast about 2 months.

In one aspect, the stick product essentially provides 3 different typesof lipstick to the user, either single-coat or double-coat.

TABLE 42 Phase Component Weight percent A ETPEA 18 Castor oil 8Hydrogenated isoparaffin 5 Isononyl isononanoate 5 Phenyltrimethylsiloxytrisiloxane 8 Copolymer vinylpyrrolidone/1-eicosene 2 BPigments (iron oxide) 10 Hydrogenated isoparaffin 5 Liquid lanolin 5Poly(12-hydroxystearic) acid 2 (Avecia SOLSPERSE ™ 21 000) C Isododecane22 Nonafluoromethoxybutane 5 Decamethyltetrasiloxane 5

Example 63 Lipstick

Utilizing the components and amounts set forth in Table 43, a cosmeticcomposition was prepared following the procedure of Examples 61 and 62.In one aspect the resulting stick product is a mono-product, one thatdeposits a single film that is, in various aspects, glossy, with reducedclinging properties, and with reduced transferability properties.Preferably, the stick does not exude at ambient temperature for a periodlasting at least about 2 months.

TABLE 43 Phase Component Weight percent A ETPEA 18.0 Fluorinatedsilicone (Shin Etsu X22819) 5.0 B Pigments (iron oxide) 10.0Poly(12-hydroxystearic) acid 1.3 (Avecia SOLSPERSE ™ 21 000) C Parleam13.8 Isononyl isononanoate q.s. 100.0

Example 64 Mascara

A mascara composition is prepared by blending the components and amountsset forth in Table 44. In one aspect, the mascara composition of thepresent invention adheres well to the eyelashes during and afterapplication. In another aspect, the mascara composition of the presentinvention gives good instantaneous loading of the eyelashes.

TABLE 44 Component Weight percent Beeswax 7.1 Hydrogenated jojoba oil7.1 ETPEA 0.5 Polybutylene 1.0 Copolymer hydroxyethylcellulose/ 3.8diallyl dimethyl ammonium chloride (National Starch CELQUAT ™ LOR)Glycerol mono- and distearate 2.1 (Goldschmidt TEGIN ™ M) PEG-30glyceryl monostearate 5.5 (Goldschmidt TAGAT ™ S) Black iron oxide 7.0Preservatives q.s. Water q.s. 100.0

Example 65 Mascara

(A) A microdispersion of carnauba wax is prepared having the compositionindicated in Table 45:

TABLE 45 Component Weight percent Carnauba wax 27.00 PEG-30 glycerylmonostearate 6.75 (Goldschmidt TAGAT ™ S) Ethanol 10.00 Water q.s.100.00

The wax and surfactant (PEG-30 glyceryl monostearate) are heated to 90°C. while homogenizing the mixture under moderate agitation. One can thenadd water heated to 90° C. to the mixture, with continued agitation.After cooling the mixture down to ambient temperature, ethanol is addedto obtain a microdispersion of wax, the particles of which have anaverage diameter of about 170 nm in one aspect.

(B) A mascara is prepared having the composition provided in Table 46.

TABLE 46 Weight Component percent Wax microdispersion of (A) above 5.0Carnauba wax 1.5 Beeswax 3.6 Paraffin wax 11.5 Hydrogenated jojoba oil0.2 Hydrogenated palm oil 0.2 ETPEA 0.5 2-Amino-2-methyl-1,3-propanediol0.8 Triethanolamine 2.4 Stearic acid 6.6 Hydroxyethylcellulose 0.8 Gumarabic 0.6 Copolymer ethyl acrylate/methyl 5.0 AM methacrylate (80/20)as an aqueous dispersion containing 50% AM (Saito DAITOSOL ™ 5000 AD)Black iron oxide 7.0 Preservatives q.s. Water q.s. 100.00

Example 66 Mascara

A mascara composition is prepared by blending the components and amountsset forth in Table 47.

TABLE 47 Weight Component percent Carnauba wax 2.9 Beeswax 3.6 Paraffinwax 11.5 Hydrogenated jojoba oil 0.2 Hydrogenated palm oil 0.2 ETPEA 2.02-Amino-2-methyl-1,3-propanediol 0.8 Triethanolamine 2.4 Stearic acid6.6 Hydroxyethylcellulose 0.8 Gum arabic 0.6 Copolymer ethylacrylate/methyl 2.5 AM methacrylate (80/20) as an aqueous dispersioncontaining 50% AM (Saito DAITOSOL ™ 5000 AD) Black iron oxide 7.0Preservatives q.s. Water q.s. 100.00

Example 67 Anhydrous Lipstick with an Opaque Base

With reference to the ingredients in Table 48, a lipstick can beprepared as follows. ETPEA, waxes and oils are charged to a reactionvessel and the mixture is heated until homogeneous. The reaction vesselis further charged with colorant, and the reaction mixture is furtherhomogenized under magnetic agitation for about 1 hour. The reactioncomposition is then poured into a mold kept at an elevated temperature(e.g., about 45° C.) to form a stick product. Once the stick productbegins to take shape, the product is allowed to congeal by resting atabout −21° C. for about 15 minutes.

The transmittance at 530 nm (i.e., the λ_(max) of coloring) of a sample(about 10 μm thick) of the composition of the lipstick above ismeasured. In one aspect the lipstick has an opaque appearance and givesa transparent cosmetic deposit conferring a pink fuchsia color to thelips. In one aspect the color deposited is very intense.

TABLE 48 Component Weight percent Propoxylated beeswax 14.5Microcrystalline wax 3.0 Propoxylated lanolin wax 2.0 Sesame oil 10.0Arara oil 18.0 Lanolin 20.0 Acetylated lanolin 6.0 Phytocos MMB RED ®Complex 33/3 0.2 colorant (active colorant matter) ETPEA q.s. Oleylerucate q.s. 100.0

Example 68 Anhydrous Lipstick with a Transparent Base

With reference to the ingredients in Table 49, a lipstick can beprepared as follows. ETPEA and oils are charged to a reaction vessel andthe mixture is heated until the ETPEA is melted and the reaction mixturebecomes transparent and homogeneous. The reaction vessel is furthercharged with colorant, and the reaction mixture is further homogenizedunder magnetic agitation for about 1 hour. The reaction composition isthen poured into a mold kept at an elevated temperature (e.g., about 45°C.) to form a stick product. Once the stick product begins to takeshape, the product is allowed to congeal by resting at about −21° C. forabout 15 minutes.

The transmittance at 530 nm (i.e., the λ_(max) of coloring) of a sample(about 10 μm thick) of the composition of the lipstick above ismeasured. In one aspect the resulting lipstick composition istranslucent, and when the stick is applied to a substrate, deposits atransparent streak of pink color

TABLE 49 Component Weight percent ETPEA 25.0 Octyldodecanol 10.0Phytocos MMB RED ® Complex 33/3 0.2 colorant (active colorant matter)Parleam oil q.s. 100.0

Example 69 Lipstick

Using the components identified in Table 50, a lipstick composition canbe prepared as follows. ETPEA and oil are charged to a reaction vesseland the mixture is heated until the ETPEA is melted and the reactionmixture becomes transparent and homogeneous. The reaction vessel isfurther charged with colorant, and the reaction mixture is furtherhomogenized under magnetic agitation for about 1 hour. The reactioncomposition is then poured into a mold kept at an elevated temperature(e.g., about 45° C.) to form a stick product. Once the stick productbegins to take shape, the product is allowed to congeal by resting atabout −21° C. for about 15 minutes.

The transmittance at 498 nm (i.e., the λ_(max) of coloring) of a sample(about 10 μm thick) of the composition of the lipstick above ismeasured. In one aspect the resulting lipstick composition istranslucent, and when the stick is applied to a substrate, deposits atransparent streak of orange color

TABLE 50 Component Weight percent ETPEA 25.0 Octyldodecanol 10.0 ROCOU ®0.2 colorant* (active colorant matter) Parleam oil q.s. 100.0 *ROCOU ®is a solution at 4% of rocou seeds in soybean oil, fromWarner-Jenkinson.

Example 70 Mascara

A mascara composition is prepared by blending the components and amountsset forth in Table 51.

TABLE 51 Component Weight percent ETPEA 0.5 Carnauba wax 2.9 Beeswax 3.6Paraffin wax 11.4 2-Amino-2-methyl-1,3-propanediol 0.5 Triethanolamine2.4 Stearic acid 5.8 Non-ionic hydrosoluble polymers 4.3 Sodiumpolymethacrylate 0.25 AM (Vanderbilt DARVAN ™ 7) JR 400 modifiedhydroxyethylcellulose 0.1 (Union Carbide) Pigments 5.4 Preservativesq.s. Water q.s. 100.0

Example 71 Waterproof Mascara

A mascara composition is prepared by blending the components and amountsset forth in Table 52.

TABLE 52 Component Weight percent ETPEA 0.5 Carnauba wax 4.7 Beeswax 4.9Paraffin wax 2.3 Sodium deoxyribonucleate 0.2 Bentonite 5.3 Propylenecarbonate 1.7 Copolymer vinylpyrrolidone/1-eicosene 2.0 Sodiumpolymethacrylate 0.25 AM (Vanderbilt DARVAN ™ 7) JR 400 modifiedhydroxyethylcellulose 0.1 (Union Carbide) Copolymer vinyl acetate/allylstearate (65/35) 2.2 (Chimex MEXOMERE ™ PQ) Vinyl polylaurate 0.7(Chimex MEXOMERE ™ PP) Rice starch 1.5 Pigments 4.2 Water 8.4 Ethylalcohol 2.0 Preservatives q.s. Isododecane q.s. 100.00

Example 72 Lipstick

With reference to Table 53, ETPEA is dissolved in octyldodecanol andparleam oil, at about 100° C., before adding pigments and fillers. Thismixture is then combined with a preheated mixture of the waxes and oils(preheated to about 90° C.). All other ingredients are added, and theentire mixture is mixed with the aid of a deflocculating (Raynerie)turbine, then poured into lipstick molds.

TABLE 53 Component Weight percent ETPEA 22.6 Parleam oil 32.7Octyldodecanol 11.3 Poly(12-hydroxystearic) acid 2.5 Pigments 10.9Lanolin (pasty) 6.3 Waxes 3.8 Fillers 3.8 Phenyl silicone (oil) 6.3

Example 73 Lipstick

With reference to the components and amounts set forth in Table 54,ETPEA is dissolved in polyglyceryl-2 polyhydroxystearate and parleamoil, at about 100° C., before adding pigments. This mixture is mixedwith the aid of a deflocculating (Raynerie) turbine, then poured intolipstick molds. The hardness of the product may be measured using atexture analyzer TA-XT2 at 20° C.

TABLE 54 Component Weight percent ETPEA 25 Parleam oil 56 Polyglyceryl-2polyhydroxystearate 10 Pigments (brown iron oxide + titanium oxide) 9

Example 74 Anhydrous Eye Shadow

Following the procedure of Example 73, but using the components of Table55, an anhydrous eye shadow was prepared.

TABLE 55 Component Weight percent ETPEA 25.00 Parleam oil 35.10 Glyceryloleate 31.25 Pigments q.s. 100.00

Throughout the present specification, where resins or reaction mixturesare described as including or comprising specific components ormaterials, it is contemplated by the inventors that the resins orreaction mixtures of the present invention also consist essentially of,or consist of, the recited components or materials. Accordingly,throughout the present disclosure any described composition (resin orreaction mixture) of the present invention can consist essentially of,or consist of, the recited components or materials.

All publications and patent applications mentioned in this specificationare herein incorporated by reference to the same extent as if eachindividual publication or patent application was specifically andindividually incorporated by reference. This includes the parentapplication, U.S. application Ser. No. 09/855,737 filed May 14, 2001.

It will be appreciated by those skilled in the art that changes could bemade to the embodiments described above without departing from the broadinventive concept thereof. It is understood, therefore, that thisinvention is not limited to the particular embodiments disclosed, but itis intended to cover modifications within the spirit and scope of thepresent invention as defined by the appended claims.

1. A personal care composition, comprising i) a resin compositionprepared by reacting components comprising dibasic acid, diamine, polyoland monoalcohol, wherein (a) at least 50 equivalent percent of thedibasic acid comprises polymerized fatty acid; (b) at least 50equivalent percent of the diamine comprises ethylene diamine; (c) 10-60equivalent percent of the total of the hydroxyl and amine equivalentsprovided by diamine, polyol and monoalcohol are provided by monoalcohol;and (d) no more than 50 equivalent percent of the total of the hydroxyland amine equivalents provided by diamine, polyol and mono alcohol areprovided by polyol; and ii) a non-aqueous phase.
 2. The compositionaccording to claim 1, wherein the non-aqueous phase comprises a liquidfatty phase.
 3. The composition according to claim 1, wherein thenon-aqueous phase comprises from 5% to 99% by weight of liquid fattyphase based upon the total weight of said composition.
 4. Thecomposition according to claim 1, wherein the non-aqueous phasecomprises from 20% to 75% by weight of liquid fatty phase based upon thetotal weight of said composition.
 5. The composition according to claim2, wherein the liquid fatty phase comprises at least one apolar oil. 6.The composition according to claim 2, wherein the liquid fatty phasecomprises at least one member selected from the group consisting ofparleam oil, isoparaffin, and squalane.
 7. The composition according toclaim 2, wherein the liquid fatty phase comprises at least 40 wt % of atleast one apolar oil based upon the total weight of the liquid fattyphase.
 8. The composition according to claim 2, wherein the liquid fattyphase comprises at least 50 wt % of at least one apolar oil based uponthe total weight of the liquid fatty phase.
 9. The composition accordingto claim 1, wherein the non-aqueous phase comprises at least one oil.10. The composition according to claim 1, wherein the non-aqueous phasecomprises at least one oil that is selected from the group consisting ofa hydrocarbon oil, synthetic oil, mineral oil, animal-derived oil,vegetable oil, and ester-containing oil.
 11. The composition accordingto claim 1, wherein the non-aqueous phase comprises at least onefluorinated or silicone containing oil.
 12. The composition according toclaim 1, wherein the non-aqueous phase comprises at least onefluorinated or silicone containing oil that is selected from the groupconsisting of a hydrocarbon oil, mineral oil, animal-derived oil,vegetable oil, and ester-containing oil.
 13. The composition accordingto claim 1, wherein the non-aqueous phase comprises at least one oil atan amount ranging from 1% to 65% by weight, relative to the total weightof the composition.
 14. The composition according to claim 1, whereinthe non-aqueous phase comprises at least one amphiphilic compound. 15.The composition according to claim 1, wherein the non-aqueous phasecomprises at least one amphiphilic compound having an HLB value in therange of from 1 to
 16. 16. The composition according to claim 1, whereinthe non-aqueous phase comprises at least one amphiphilic compound havingan HLB value that is less than
 8. 17. The composition according to claim1, wherein the non-aqueous phase comprises from 0.1% to 35% by weight ofat least one amphiphilic compound, of the total weight of saidcomposition.
 18. The composition according to claim 1, wherein thenon-aqueous phase comprises from 2% to 15% by weight of at least oneamphiphilic compound, of the total weight of said composition.
 19. Thecomposition according to claim 1, wherein the non-aqueous phasecomprises at least one amphiphilic compound in the form of a wax, anoil, or mixtures thereof.
 20. The composition according to claim 1,wherein the non-aqueous phase comprises the resin composition.
 21. Thecomposition according to claim 1, wherein the non-aqueous phasecomprises at least one member selected from the group consisting of aliquid fatty phase, an oil, and an amphiphilic compound.